Curable composition

ABSTRACT

An object of the present invention is to provide a curable composition that can be used as sealing materials, adhesives, and the like, has excellent curing properties, and gives a cured product excellent in elongation properties. The object can be attained by means of a curable composition comprising: a reactive silyl group-containing polyether polymer (A) that contains a reactive silyl group with high activity (e.g., (ClCH 2 )(CH 3 O) 2 Si—, (CH 3 OCH 2 )(CH 3 O) 2 Si—, or CH 3 (CH 3 O) 2 Si—CH 2 —NH—C(═O)—); and a reactive silyl group-containing polyether polymer (B) that contains a reactive silyl group (e.g., CH 3 (CH 3 O) 2 Si— or (CH 3 O) 3 Si—) different from that mentioned above and/or a (meth)acrylic polymer (C) containing a reactive silyl group that is not particularly limited.

TECHNICAL FIELD

The present invention relates to an organic polymer containing asilicon-containing group which contains a hydroxy or hydrolyzable groupbonded to a silicon atom and can form a siloxane bond to be cross-linked(hereinafter referred to also as a “reactive silyl group”), and acurable composition comprising the organic polymer.

BACKGROUND ART

An organic polymer having at least one reactive silyl group per moleculeis known to have a characteristic that it is crosslinked by siloxanebond formation involving hydrolysis or other reactions of the silylgroup due to factors such as moisture even at room temperature, wherebya rubbery cured product is obtained.

Among such polymers, polymers containing an alkyldialkoxysilyl group areknown to offer excellent, flexible and tough cured products and arewidely used in applications such as sealants, adhesives, and coatingagents. Curable compositions containing these organic polymers areusually cured by means of a condensation catalyst such as a dibutyltincompound. In the case that such a curable composition needs to be curedin a short time, generally, for example, the amount of condensationcatalyst is increased. However, the toxicity of organotin compounds hasbeen pointed out in recent years, and these compounds must be used withcare from the viewpoint of environmental safety.

Although polymers having a trialkoxysilyl group at both terminals havehigh curability, the resulting cured products are known to be hard andbrittle. In the case of using these polymers for contact adhesives, thecrosslink density becomes too high during curing, which causes theproblem that the length of time until tack development (i.e., so-calledopen time) cannot be long.

Meanwhile, it has been suggested that the use of a polymer having aspecific terminal structure, although terminated with a dialkoxysilylgroup, can provide a curable composition having a high curing rate(Patent Literature 1 and Patent Literature 2). In some cases, however,the curable compositions prepared from the polymers described in PatentLiteratures 1 and 2 give cured products having poor tensile properties.

CITATION LIST Patent Literature

-   Patent Literature 1: JP-T 2005-501146-   Patent Literature 2: WO2008/053875

SUMMARY OF INVENTION Technical Problem

Use of the polymers proposed by Patent Literature 1 and PatentLiterature 2 can provide curable compositions having high curability,even if, for example, an amine compound is used as the condensationcatalyst. Depending on applications, however, elongation properties maybe required. Thus, these curable compositions still leave room forimprovement in terms of obtaining both elongation properties andcurability.

An object of the present invention is to provide a curable compositionthat has excellent elongation properties and rapid curability even whena non-organotin condensation catalyst is used, and has a long tack timewhen used as a contact adhesive.

Another object of the present invention is to provide a curablecomposition that has a curing rate as rapid as the curability of thepolymers described in the aforementioned patent literatures withoutimpairing the elongation properties of a polymer containing analkyldialkoxysilyl group, and has a long tack time.

Solution to Problem

As a result of eager studies to solve the problems, the presentinventors have found that the use of an organic polymer (A) containing areactive silyl group having a specific structure, together with areactive silyl group-containing polyether polymer (B) and/or a reactivesilyl group-containing (meth)acrylic polymer (C) makes it possible toachieve both excellent elongation properties and initial tack propertieswithout impairing the rapid curability of the polymer (A). Based on thefindings, the present invention has been completed.

Specifically, the present invention is directed to:

(1) a curable composition, comprising:

a polyether polymer (A) containing a reactive silyl group represented bythe following formula (1); and

at least one of a polyether polymer (B) containing a reactive silylgroup represented by the following formula (2), and a (meth)acrylicpolymer (C) containing a reactive silyl group represented by thefollowing formula (3):—W—CH₂—SiR¹ _(a)R² _(b)X_(c)   (1)

wherein R¹ is a C1 to C20 hydrocarbon group wherein at least onehydrogen atom on carbon atoms at positions 1 to 3 is replaced withhalogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷ (in which each of R³, R⁴, R⁵, and R⁷is a hydrogen atom or a C1 to C20 substituted or unsubstitutedhydrocarbon group, and R⁶ is a divalent C1 to C20 substituted orunsubstituted hydrocarbon group), a C1 to C20 perfluoroalkyl group, or acyano group; R² represents a C1 to C20 hydrocarbon group, a C6 to C20aryl group, a C7 to C20 aralkyl group, or a triorganosiloxy grouprepresented by R⁰ ₃SiO— wherein each of three R⁰s is a C1 to C20hydrocarbon group and they may be the same as or different from eachother; X represents a hydroxy or hydrolyzable group; W represents alinking group selected from —O—R⁸—, —O—CO—N(R⁹)—, —N(R⁹)—CO—O—,—N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁸ represents adivalent C1 to C8 hydrocarbon group, and R⁹ represents hydrogen or a C1to C18 hydrocarbon group optionally substituted with halogen; in thecase that W is —O—R⁸—, a is 1 or 2, b is 0 or 1, and c is 1 or 2,provided that a+b+c=3 is satisfied; in the case that W is a group otherthan —O—R⁸—, a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3,provided that a+b+c=3 is satisfied; and in the case that a plurality ofR¹s, R²s, or Xs exist, they may be the same as or different from eachother,—V—SiR² _(d)X_(3-d)   (2)

wherein R² and X are defined as mentioned in formula (1); V represents adivalent C2 to C8 hydrocarbon group; d represents any of 0, 1, and 2;and in the case that a plurality of R²s or Xs exist, they may be thesame as or different from each other, and—Z—(CH₂)_(n)—SiR¹ _(a)R² _(b)X_(c)   (3)

wherein R¹, R², and X are defined as mentioned in formula (1); Zrepresents a linking group selected from —CO—O—, —O—CO—N(R⁹)—,—N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁹is defined as mentioned in formula (1); n represents a number of 1 to 8;a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that thecondition: a+b+c=3 is satisfied; and in the case that a plurality ofR¹s, R²s, or Xs exist, they may be the same as or different from eachother;

(2) the curable composition according to (1),

wherein R¹ in formula (1) is an organic group represented by thefollowing formula (4):—CR¹⁰ _(3-e)Y_(e)   (4)

wherein Y is a group selected from halogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷(in which each of R³, R⁴, R⁵, and R⁷ is a hydrogen atom or a C1 to C20substituted or unsubstituted hydrocarbon group, and R⁶ is a divalent C1to C20 substituted or unsubstituted hydrocarbon group), a C1 to C20perfluoroalkyl group, and a cyano group; R¹⁰ represents a hydrogen atomor a C1 to C19 alkyl group; e represents 1, 2, or 3; and in the casethat a plurality of Ys or R¹⁰s exist, they may be the same as ordifferent from each other;

(3) the curable composition according to (2),

wherein Y in formula (4) is chlorine;

(4) the curable composition according to (2),

wherein the group represented by formula (4) is a chloromethyl group;

(5) the curable composition according to (2),

wherein Y in formula (4) is an alkoxy group;

(6) the curable composition according to (2),

wherein Y in formula (4) is at least one group selected from the groupconsisting of a methoxy group, an ethoxy group, and a phenoxy group;

(7) the curable composition according to (2),

wherein the group represented by formula (4) is a methoxymethyl group;

(8) the curable composition according to any one of (1) to (7),

wherein W in formula (1) is —O—R⁸— in which R⁸ is a divalent C1 to C8hydrocarbon group;

(9) the curable composition according to any one of (1) to (8),

wherein the polyether polymer (A) is a polyoxypropylene polymer;

(10) the curable composition according to any one of (1) to (9),

wherein the polyether polymer (A) is a linear polymer having no branch;

(11) the curable composition according to any one of (1) to (10),

wherein a backbone structure of the polyether polymer (B) is apolyoxypropylene polymer;

(12) the curable composition according to any one of (1) to (11),

wherein the reactive silyl group of formula (2) is adimethoxymethylsilyl group;

(13) the curable composition according to any one of (1) to (12),

wherein the (meth)acrylic polymer (C) is at least one of a reactivesilyl group-containing alkyl(meth)acrylate polymer and copolymer;

(14) the curable composition according to (1) to (13),

which comprises the polyether polymer (A), the polyether polymer (B),and the (meth)acrylic polymer (C);

(15) the curable composition according to (1) to (14),

wherein the polyether polymer (A) has a number average molecular weightof 22,000 or higher;

(16) the curable composition according to any one of (1) to (15),

wherein the polyether polymer (A) and the polyether polymer (B) arecontained at a ratio of (A):(B)=50:50 to 5:95 (parts by weight);

(17) the curable composition according to any one of (1) to (16),further comprising:

at least one of an amine compound (d1) and an organic dialkyltincompound (d2) as a condensation catalyst (D);

(18) a sealing material, comprising the curable composition according toany one of (1) to (17) as a component;

(19) an adhesive, comprising the curable composition according to anyone of (1) to (17) as a component;

(20) a contact adhesive, comprising the curable composition according toany one of (1) to (17) as a component;

(21) the contact adhesive according to any one of (1) to (17),comprising the polyether polymer (A) and the polyether polymer (B); and

(22) a cured product, obtained by curing the curable compositionaccording to any one of (1) to (17).

Advantageous Effects of Invention

The curable composition of the present invention comprising the reactivesilyl group-containing polyether polymer (A), and the reactive silylgroup-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer has excellent elongationproperties and rapid curability and is also excellent in initial tackproperties.

DESCRIPTION OF EMBODIMENTS

Hereinafter, the present invention will be described in detail.

(Reactive Silyl Group-Containing Polyether Polymer (A))

The reactive silyl group-containing polyether polymer (A) in the presentinvention is an organic polymer containing a reactive silyl grouprepresented by the following formula (1):—W—CH₂—SiR¹ _(a)R² _(b)X_(c)   (1)

wherein R¹ represents a C1 to C20 hydrocarbon group wherein at least onehydrogen atom on carbon atoms at positions 1 to 3 is replaced withhalogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷ (in which each of R³, R⁴, R⁵, and R⁷is a hydrogen atom or a C1 to C20 substituted or unsubstitutedhydrocarbon group, and R⁶ is a divalent C1 to C20 substituted orunsubstituted hydrocarbon group), a C1 to C20 perfluoroalkyl group, or acyano group; R² represents a C1 to C20 hydrocarbon group, a C6 to C20aryl group, a C7 to C20 aralkyl group, or a triorganosiloxy grouprepresented by R⁰ ₃SiO— wherein each of three R⁰s is a C1 to C20hydrocarbon group and they may be the same as or different from eachother; X represents a hydroxy or hydrolyzable group; W represents alinking group selected from —O—R⁸—, —O—CO—N(R⁹)—, —N(R⁹)—CO—O—,—N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁸ represents adivalent C1 to C8 hydrocarbon group, and R⁹ represents hydrogen or a C1to C18 hydrocarbon group optionally substituted with halogen; in thecase that W is —O—R⁸—, a is 1 or 2, b is 0 or 1, and c is 1 or 2,provided that the condition: a+b+c=3 is satisfied; in the case that W isa group other than —O—R⁸—, a is 0, 1, or 2, b is 0, 1, or 2, and c is 1,2, or 3, provided that the condition: a+b+c=3 is satisfied; and in thecase that a plurality of R¹s, R²s, Xs, Ws, or R⁹s exist, they may be thesame as or different from each other.

(Regarding Reactive Silyl Group of Formula (1))

(I) In the Case that the Linking Group W in Formula (1) is —O—R⁸—:

The substituents bonded to the silicon atom in formula (1) require ahydrolyzable or hydroxy group as well as a hydrocarbon group wherein atleast one hydrogen atom on carbon atoms at positions 1 to 3 is replacedwith halogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷ (in which each of R³, R⁴, R⁵,and R⁷ is a hydrogen atom or a C1 to C20 substituted or unsubstitutedhydrocarbon group, and R⁶ is a divalent C1 to C20 substituted orunsubstituted hydrocarbon group), a C1 to C20 perfluoroalkyl group, or acyano group. By virtue of the reactive silyl group represented byformula (1), the polyether polymer (A) in the present invention exhibitsrapid curability, compared with organic polymers containing a reactivesilyl group that contains an unsubstituted hydrocarbon group such as amethyl group (e.g., a dimethoxymethylsilyl group).

For higher curability, R¹ in formula (1) is more preferably asubstituent represented by the following formula (4):—CR¹⁰ _(3-e)Y_(e)   (4)

wherein Y is a group selected from halogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷(in which each of R³, R⁴, R⁵, and R⁷ is a hydrogen atom or a C1 to C20substituted or unsubstituted hydrocarbon group, and R⁶ is a divalent C1to C20 substituted or unsubstituted hydrocarbon group), a C1 to C20perfluoroalkyl group, and a cyano group; R¹⁰ represents a hydrogen atomor a C1 to C19 alkyl group; e represents 1, 2, or 3; in the case that aplurality of R¹⁰s or Ys exist, they may be the same as or different fromeach other.

The substituent represented by formula (4) is one kind of R¹ in formula(1) and represents a hydrocarbon group having a heteroatom atposition 1. In the case that two or more R¹⁰s exist, the total number ofcarbon atoms in two R¹⁰s is preferably 0 to 19.

Examples of Y in formula (4) include, but not limited to: halogens;oxygen-containing substituents such as alkoxy groups and acyloxy groups;nitrogen-containing substituents such as amino groups, alkylaminogroups, and ureido groups; a cyano group; and perfluoroalkyl groups.

More specific examples thereof include: halogens such as fluorine,chlorine, bromine, and iodine; alkoxy groups such as a methoxy group, anethoxy group, a 1-propoxy group, a 2-propoxy group, a 1-butoxy group, a2-butoxy group, a tert-butyloxy group, an octoxy group, a lauryloxygroup, a phenoxy group, and a benzyloxy group; acyloxy groups such as anacetoxy group, a propanoyloxy group, and a benzoyloxy group; an aminogroup and substituted amino groups such as a methylamino group, adimethylamino group, an ethylamino group, a diethylamino group, apropylamino group, a dipropylamino group, and a diphenylamino group;groups containing moieties bonded via a urethane or urea bond, such asan ureido group and a carbamate group; acyl groups such as an acetylgroup, a propanoyl group, an octanoyl group, a lauroyl group, and abenzoyl group; alkoxycarbonyl groups such as a methoxycarbonyl group anda tert-butyloxycarbonyl group; a nitro group; a cyano group; anisocyanato group; sulfonyl groups such as a methylsulfonyl group and atoluenesulfonyl group; perfluoroalkyl groups such as a trifluoromethylgroup, a pentafluoroethyl group, a perfluoropropyl group, aperfluorohexyl group, and a perfluorooctyl group; andelectron-withdrawing aryl groups such as a difluorophenyl group and apentafluorophenyl group. Preferred among these are halogens, alkoxygroups, substituted or unsubstituted amino groups, and a trifluoromethylgroup, because the resulting polymer exhibits high curability. Morepreferred are halogens, alkoxy groups, and substituted or unsubstitutedamino groups, and still more preferred are halogens and alkoxy groups.In particular, chlorine or a methoxy group is preferred in terms of highcurability in the presence of an amine compound as the curing catalyst.Also, a dialkylamino group is preferred in terms of high curability inthe presence of a curing catalyst such as carboxylic acids.

Examples of R¹ in formula (1) include, but not limited to, afluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a3,3,3-trifluoropropyl group, a chloromethyl group, a dichloromethylgroup, a 1-chloroethyl group, a 2-chloroethyl group, a 3-chloropropylgroup, a 2-chloropropyl group, a 1-chloropropyl group, a bromomethylgroup, an iodomethyl group, a 3-iodopropyl group, a methoxymethyl group,a 1-methoxyethyl group, an ethoxymethyl group, a phenoxymethyl group, anaminomethyl group, an N-methylaminomethyl group, anN,N-dimethylaminomethyl group, an N-ethylaminomethyl group, anN,N-diethylaminomethyl group, an acetoxymethyl group, a methylcarbamategroup, and a 2-cyanoethyl group.

X in formula (1) represents a hydroxy or hydrolyzable group. Thehydrolyzable group is not particularly limited and may be aconventionally known hydrolyzable group such as hydrogen, halogen, analkoxy group, an acyloxy group, a ketoxymate group, an amino group, anamido group, an acid amido group, an aminooxy group, a mercapto group,and an alkenyloxy group. Preferred among these are a hydrogen atom, analkoxy group, an acyloxy group, a ketoxymate group, an amino group, anamido group, an aminooxy group, a mercapto group, and an alkenyloxygroup. In terms of mild hydrolysis and easy workability, more preferredare alkoxy groups such as a methoxy group and an ethoxy group, andparticularly preferred are a methoxy group and an ethoxy group.

The reactive silyl group represented by formula (1) preferably has twohydrolyzable or hydroxy groups because rapid curability is then likelyto be obtained.

Examples of R² in formula (1) include, but not limited to: alkyl groupssuch as a methyl group and an ethyl group; cycloalkyl groups such as acyclohexyl group; aryl groups such as a phenyl group; and aralkyl groupssuch as a benzyl group. Among these, a methyl group is particularlypreferred.

Examples of the reactive silyl group of formula (1) include, but notlimited to, a (chloromethyl)methoxymethylsilyl group, abis(chloromethyl)methoxysilyl group, a (chloromethyl)dimethoxysilylgroup, a (chloromethyl)diethoxysilyl group, a(dichloromethyl)dimethoxysilyl group, a (1-chloroethyl)dimethoxysilylgroup, a (1-chloropropyl)dimethoxysilyl group, a(methoxymethyl)dimethoxysilyl group, a (1-methoxyethyl)dimethoxysilylgroup, a (methoxymethyl)diethoxysilyl group, an(ethoxymethyl)dimethoxysilyl group, an (ethoxymethyl)diethoxysilylgroup, an (aminomethyl)dimethoxysilyl group, a (dimethylaminomethyl)dimethoxysilyl group, a (diethylaminomethyl)dimethoxysilyl group, a(diethylaminomethyl)diethoxysilyl group, anN-(2-aminoethyl)aminomethyldimethoxysilyl group, a(1-aminopropyl)dimethoxysilyl group, a(1-(N-methylamino)propyl)dimethoxysilyl group, a(1-(N,N-dimethylamino)propyl)dimethoxysilyl group, a(3-(2-aminoethyl)aminopropyl)dimethoxysilyl group, a(1-(3,3,3-trifluoro)propyl)dimethoxysilyl group, an(acetoxymethyl)dimethoxysilyl group, and an (acetoxymethyl)diethoxysilylgroup. Preferred among these are a (chloromethyl)dimethoxysilyl group, a(methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilylgroup, a (diethylaminomethyl)diethoxysilyl group, and a(1-(3,3,3-trifluoro)propyl)dimethoxysilyl group, in terms of their easysynthesis. More preferred are a (chloromethyl)dimethoxysilyl group, a(methoxymethyl)dimethoxysilyl group, and a(diethylaminomethyl)diethoxysilyl group, because they provide curedproducts with a higher degree of curing. Particularly preferred are a(chloromethyl)dimethoxysilyl group and a (methoxymethyl)dimethoxysilylgroup.

In the case that the linking group W is —O—R⁸—, specific examples of R⁸include divalent hydrocarbon linking groups such as —CH₂—, —CH₂CH₂—,—CH₂CH₂CH₂—, and —CH₂CH₂CH₂CH₂—.

(II) In the Case that the Linking Group W in Formula (1) is not —O—R⁸—:

The polymer end of the polyether polymer (A) is required to be bonded tothe silicon atom in the reactive silyl via a linking group representedby the following formula (5), or in other words the —W—CH₂— in formula(1) is required to be represented by the following formula (5):—W¹—CH₂—  (5)

wherein W¹ represents a linking group selected from —O—CO—N(R⁹)—,—N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁹represents hydrogen or a C1 to C18 hydrocarbon group optionallysubstituted with halogen.

Such a polyether polymer (A) in which a specific linking group isintroduced in the present invention exhibits rapid curability, comparedwith an organic polymer in which the silicon atom in a reactive silyl isbonded to the polymer end of the organic polymer via a C2 or higherhydrocarbon group.

Specifically, the linking group -W-CH₂— in formula (1) is —W¹—CH₂— when,for example, an organic polymer terminated with any of a hydroxy group,an isocyanato group, a thiol group and an amino group is allowed toreact with a silane compound containing an isocyanatomethyl group and ahydrolyzable group (e.g., 1-isocyanatomethyl-trimethoxysilane,1-isocyanatomethyl-triethoxysilane,1-isocyanatomethyl-dimethoxymethylsilane,1-isocyanatomethyl-diethoxymethylsilane).

When the linking group W in formula (1) is not —O—R⁸—, specific examplesof the structure of the group represented by —SiR¹ _(a)R² _(b)X_(c) informula (1) include a (chloromethyl)methoxymethylsilyl group, abis(chloromethyl)methoxysilyl group, a (chloromethyl)dimethoxysilylgroup, a (chloromethyl)diethoxysilyl group, a(dichloromethyl)dimethoxysilyl group, a (chloroethyl)dimethoxysilylgroup, a (chloropropyl)dimethoxysilyl group, a(methoxymethyl)dimethoxysilyl group, a (methoxymethyl)diethoxysilylgroup, an (ethoxymethyl)dimethoxysilyl group, an(aminomethyl)dimethoxysilyl group, a (dimethylaminomethyl)dimethoxysilylgroup, a (diethylaminomethyl)dimethoxysilyl group, a(diethylaminomethyl)diethoxysilyl group, an(N-(2-aminoethyl)aminomethyl)dimethoxysilyl group, a(1-aminopropyl)dimethoxysilyl group, a(1-(N-methylamino)propyl)dimethoxysilyl group, a(1-(N,N-dimethylamino)propyl)dimethoxysilyl group, a3-(2-aminoethyl)aminopropyldimethoxysilyl group, a(3,3,3-trifluoropropyl)dimethoxysilyl group, an(acetoxymethyl)dimethoxysilyl group, and an (acetoxymethyl)diethoxysilylgroup, a methyldimethoxysilyl group, a methyldiethoxysilyl group, amethyldiisopropoxysilyl group, a trimethoxysilyl group, a triethoxysilylgroup, a triisopropoxysilyl group, a methoxydimethylsilyl group, and anethoxydimethylsilyl group. More preferred among these are amethyldimethoxysilyl group, a methyldiethoxysilyl group, atrimethoxysilyl group, and a triethoxysilyl group, in terms of theavailability of the starting material silane compound containing anisocyanatomethyl group and a hydrolyzable group.

(Regarding Backbone Structure of Reactive Silyl Group-containingPolyether Polymer (A))

The backbone structure of the reactive silyl group-containing polyetherpolymer (A) in the present invention is not particularly limited, andthose having a backbone structure containing an ether bond can be used.

Specific examples of the backbone structure containing an ether bondinclude: polyoxyalkylene polymers such as polyoxyethylene,polyoxypropylene, polyoxybutylene, polyoxytetramethylene,polyoxyethylene-polyoxypropylene copolymers, andpolyoxypropylene-polyoxybutylene copolymers; polyester polymers obtainedby condensation of a dibasic acid such as adipic acid and a glycol, andby ring-opening polymerization of lactones; and polycarbonate polymersobtained by polycondensation of bisphenol A and carbonyl chloride.

More preferred among these are polyoxyalkylene polymers. This is becausethese polymers have a relatively low glass transition temperature, andgive cured products that are excellent in cold resistance.

Moreover, polyoxyalkylene polymers are particularly preferred becausethey have high moisture permeability and are excellent in the depthcurability when used for one-pack compositions, and in adhesion.

The glass transition temperature of the reactive silyl group-containingpolyether polymer (A) in the present invention is not particularlylimited, and is preferably 20° C. or lower, more preferably 0° C. orlower, and particularly preferably −20° C. or lower. The glasstransition temperature of higher than 20° C. may lead to high viscosityin winter or in cold districts and therefore to lower workability, andmay also lead to lower flexibility and lower elongation of the curedproduct. The glass transition temperature values are measured by DSC.

The polyoxyalkylene polymers are polymers containing a repeating unitrepresented by —R¹¹—O— wherein R¹¹ is a C1 to C14 linear or branchedalkylene group. R¹¹ is more preferably a C2 to C4 linear or branchedalkylene group. Specific examples of the repeating unit represented by—R¹¹—O— include —CH₂O—, —CH₂CH₂O—, —CH₂CH(CH₃)O—, —CH₂CH(C₂H₅)O—,—CH₂C(CH₃)(CH₃)O—, and —CH₂CH₂CH₂CH₂O—.

The backbone structure of the polyoxyalkylene polymer may have one kindof repeating units, or two or more kinds of repeating units.

Particularly in applications such as sealants and adhesives, thebackbone structure of the polyoxyalkylene polymer is preferably formedof a polyoxypropylene polymer having 50% by weight or more, preferably80% by weight or more, of oxypropylene repeating units based on thetotal polymer backbone structure because it is then amorphous andrelatively low in viscosity.

The backbone structure of the polyether polymer (A) is not particularlylimited and is preferably a linear polymer in terms of excellenttackiness during the initial curing, or is preferably a branched polymerbecause rapid curability is then likely to be obtained. In the case thata branch exists, the number of branches is preferably 1 to 6 (i.e. thenumber of terminal hydroxy groups is 3 to 8), more preferably 1 to 4(i.e., the number of terminal hydroxy groups is 3 to 6), and mostpreferably 1 (i.e., the number of terminal hydroxy groups is 3).

The polyoxyalkylene polymer is preferably obtained by the ring-openingpolymerization reaction of a cyclic ether compound using apolymerization catalyst in the presence of an initiator.

Examples of the cyclic ether compound include ethylene oxide, propyleneoxide, butylene oxide, tetramethylene oxide, and tetrahydrofuran. One ofthese cyclic ether compounds may be used alone, or two or more of thesemay be used in combination. Among these cyclic ether compounds, inparticular, propylene oxide is preferably used because it provides anamorphous polyether polymer with relatively low viscosity.

Specific examples of the initiator include: alcohols such as ethyleneglycol, propylene glycol, butanediol, hexamethylene glycol, neopentylglycol, diethylene glycol, dipropylene glycol, triethylene glycol,glycerol, trimethylolmethane, trimethylolpropane, pentaerythritol, andsorbitol; and polyoxyalkylene polymers having a number average molecularweight of 300 to 4,000, such as polyoxypropylene diol, polyoxypropylenetriol, polyoxyethylene diol, and polyoxyethylene triol.

The backbone structure of the reactive silyl group-containing polyetherpolymer (A) in the present invention may be a polyoxyalkylene polymercontaining other bonds such as a urethane bond or a urea bond in thebackbone structure to the extent that does not impair the effects of thepresent invention considerably. Specific examples of such polymersinclude polyurethane prepolymers.

The polyurethane prepolymers may be obtained by conventionally knownmethods and can be obtained, for example, by the reaction between apolyol compound and a polyisocyanate compound.

Specific examples of the polyol compound include polyether polyol,polyester polyol, polycarbonate polyol, and polyether polyester polyol.

Specific examples of the polyisocyanate compound include diphenylmethanediisocyanate, tolylene diisocyanate, xylylene diisocyanate,methylene-bis(cyclohexylisocyanate), isophorone diisocyanate, andhexamethylene diisocyanate.

The polyurethane prepolymer may be any of hydroxy- andisocyanato-terminated ones.

A cured product obtained from a curable composition containing a polymercontaining a urethane bond, a urea bond and/or an ester bond in thebackbone structure as the reactive silyl group-containing polyetherpolymer (A) in the present invention may have significantly reducedstrength due to possible cleavage of the backbone at the urethane bond,urea bond and/or ester bond by heat or the like.

If the reactive silyl group-containing polyether polymer (A) in thepresent invention has many amide bonds (—NR¹²—C(═O)— wherein R¹²represents a hydrogen atom or a substituted or unsubstituted organicgroup) in the backbone skeleton, the polymer is likely to have higherviscosity. Its viscosity may be increased after storage, and thus theresulting composition may have lower workability. These amide bonds mayalso be cleaved by heat or the like.

Hence, in the case that the polymer contains amide bonds in the backbonestructure, the number of amide bonds is 1 to 10, preferably 1.5 to 5,and more preferably 2 to 3, on average per molecule. The polymer havingless than one amide bond may have insufficient curability, whereas thepolymer having more than 10 amide bonds may be difficult to handle dueto its high viscosity.

For these reasons, the backbone structure of the reactive silylgroup-containing polyether polymer (A) in the present invention is mostpreferably a polyoxyalkylene polymer free from a urethane bond, a ureabond, an amide bond, an ester bond and the like linking group in thebackbone structure, from the viewpoint of providing a curablecomposition excellent in storage stability and workability.

(Regarding Method for Producing Reactive Silyl Group-containingPolyether Polymer (A))

The reactive silyl group-containing polyether polymer (A) in the presentinvention is preferably obtained by any of the following methods (a) to(c):

(a) the terminal hydroxy group of a hydroxy-terminated polymer isconverted to an unsaturated group such as an allyl group, and theresulting polymer is then reacted with a silane compound represented byHSiR¹ _(n)R² _(o)X_(p) (in which n is 1 or 2, o is 0 or 1, and p is 1 or2, provided that the condition: n+o+p=3 is satisfied; and each of R¹,R², and X is defined as mentioned in formula (1)) to obtain a reactivesilyl group-containing polyether polymer;

(b) the terminal hydroxy group of a hydroxy-terminated polymer isconverted to an unsaturated group such as an allyl group, and theresulting polymer is then reacted with dimethylchlorosilane and thenhydrolyzed to obtain a silanol-terminated polymer, which is in turnreacted with a silane compound represented by SiR¹ _(k)R² _(l)X_(m) (inwhich k is 1 or 2, l is 0 or 1, and m is 2 or 3, provided that thecondition: k+l+m=4 is satisfied; and each of R¹, R², and X is defined asmentioned in formula (1)) to obtain a reactive silyl group-containingpolyether polymer; and

(c) the terminal hydroxy group of a hydroxy-terminated polymer isreacted with an isocyanatosilane represented by OCN—CH₂—SiR¹ _(h)R²_(i)X_(j) (in which h is 0, 1, or 2, i is 0, 1, or 2, and j is 1, 2, or3, provided that the condition: h+i+j=3 is satisfied; and each of R¹,R², and X is defined as mentioned in formula (1)) to obtain a reactivesilyl group-containing polyether polymer.

Among these methods, the method (a) or (b) is preferred because thepolymer thereby obtained is less viscous than the reactivesilyl-containing organic polymer obtained by the method (c). Also, themethod (c) is preferred because it achieves a high silyl groupintroduction rate in a relatively short time.

The reactive silyl group-containing polyether polymer (A) preferably hasa molecular weight distribution (Mw/Mn) of 1.6 or less, more preferably1.5 or less, and particularly preferably 1.4 or less.

With respect to the number average molecular weight of the reactivesilyl group-containing polyether polymer (A), the lower limit ispreferably 3,000 or higher, more preferably 5,000 or higher, andparticularly preferably 8,000 or higher, and the upper limit ispreferably 100,000 or less, more preferably 50,000 or less, andparticularly preferably 35,000 or less, as determined by GPC on thepolystyrene equivalent basis. The reactive silyl group-containingpolyether polymer (A) having a higher molecular weight, when used forcontact adhesives, causes initial tack to be developed more rapidly andalso offers higher tack strength. This effect is more apparent with themolecular weight of 22,000 or higher. If the number average molecularweight is less than 3,000, a cured product formed from the reactivesilyl group-containing polyether polymer (A) is likely to have lowerelongation at break. If the number average molecular weight exceeds100,000, the curing rate is likely to be reduced due to too low aconcentration of reactive silyl groups. In addition, the reactive silylgroup-containing polyether polymer (A) is likely to be difficult tohandle due to too high viscosity.

The number of reactive silyl groups in the reactive silylgroup-containing polyether polymer (A) accounts for 50% or more, morepreferably 60% or more, and particularly preferably 60 to 85%, of allmolecular terminal groups in order to provide a favorable rubbery curedproduct. If the number of reactive silyl groups accounts for less than50% of all molecular terminal groups, the curability may beinsufficient, which makes it difficult to provide a favorable rubberelastic behavior. The number of molecular terminal groups per moleculeis preferably 2 to 8, more preferably 2 to 4, and particularlypreferably 2 or 3. The number of reactive silyl groups per molecule ispreferably 1 to 7, more preferably 1 to 3.4, and particularly preferably1 to 2.6, on average.

The reactive silyl group may be located at a backbone terminal, or at aside chain terminal, or at both terminals, of the organic polymer chain.In particular, the reactive silyl group is preferably located at abackbone terminal of the molecular chain because the molecular weightbetween crosslinks is then increased, which tends to provide a rubberycured product having higher strength, higher elongation, and lowerelastic modulus.

The average number of reactive silyl groups in the reactive silylgroup-containing polyether polymer (A) is defined as an average numberdetermined by quantifying a proton on the carbon directly bonded to eachreactive silyl group by a high-resolution ¹H-NMR measurement method.With respect to the calculation of the average number of reactive silylgroups in the reactive silyl group-containing polyether polymer (A)according to the present invention, the average number of reactive silylgroups per molecule is calculated based on the parameter (the number ofmolecules) including, as a part of members of the reactive silylgroup-containing polyether polymer (A) having the same backbonestructure, a polyether polymer precursor containing no reactive silylgroup introduced and by-products, modified polyether polymer precursorscontaining no reactive silyl group introduced after a reactive silylgroup is introduced into the polyether polymer precursor into which thereactive silyl group is introduced.

(Reactive Silyl Group-containing Polyether Polymer (B))

The reactive silyl group-containing polyether polymer (B) in the presentinvention is not particularly limited as long as it is an organicpolymer having a reactive silyl group represented by the followingformula (2) at a molecular chain terminal:—V—SiR² _(d)X_(3-d)   (2)

wherein R² and X are defined as mentioned in formula (1); V represents adivalent C2 to C8 hydrocarbon group; d represents any of 0, 1, and 2;and in the case that a plurality of R²s or Xs exist, they may be thesame as or different from each other.

(Regarding Reactive Silyl Group of Formula (2))

X in formula (2) represents a hydroxy or hydrolyzable group. Examples ofthe hydrolyzable group include, but not limited to, conventionally knownhydrolyzable groups such as the same ones as in formula (1). In terms ofmild hydrolysis and easy workability, more preferred are alkoxy groupssuch as a methoxy group and an ethoxy group, and particularly preferredare a methoxy group and an ethoxy group. The number of Xs is preferably2 in terms of curability, or is preferably 3 in terms of initial tackand because the resulting cured product has favorable rubber elasticity.

Examples of R² in formula (2) include, but not limited to, the same onesas in formula (1). A methyl group is particularly preferred.

Specific examples of the linking group V in formula (2) include divalenthydrocarbon linking groups such as —CH₂CH₂—, —CH₂CH₂CH₂—, and—CH₂CH₂CH₂CH₂—.

Specific examples of the structure of the group represented by —SiR²_(d)X_(3-d) in formula (2) include a trimethoxysilyl group, atriethoxysilyl group, a triisopropoxysilyl group, a dimethoxymethylsilylgroup, a diethoxymethylsilyl group, a diisopropoxymethylsilyl group, amethoxydimethylsilyl group, and an ethoxydimethylsilyl group. Morepreferred are a trimethoxysilyl group, a triethoxysilyl group, and adimethoxymethylsilyl group, because they have high activity to achievefavorable curability. Particularly preferred is a trimethoxysilyl group.Also, a dimethoxymethylsilyl group is particularly preferred because theresulting composition exhibits favorable initial tack and favorabletensile properties. A triethoxysilyl group is preferred in terms ofsafety because an alcohol formed along with the hydrolysis reaction ofthe reactive silyl group is ethanol.

(Regarding Backbone Structure of Reactive Silyl Group-containingPolyether Polymer (B))

The backbone structure of the reactive silyl group-containing polyetherpolymer (B) in the present invention is not particularly limited, andones having the same structure as in the reactive silyl group-containingpolyether polymer (A) can be used. Preferred among these are backbonestructures derived from polyoxypropylene diol and/or polyoxypropylenetriol, and more preferred are backbone structures derived frompolyoxypropylene diol.

(Regarding Reactive Silyl Group-containing Polyether Polymer (B))

The reactive silyl group-containing polyether polymer (B) in the presentinvention is preferably obtained by the following method (d):

(d) the terminal hydroxy group of a hydroxy-terminated polyoxyalkylenepolymer is converted to an unsaturated group such as an allyl group, andthe resulting polymer is then reacted with a silane compound representedby HSiR² _(d)X_(3-d) (in which each of R², X, and d is defined asmentioned in formula (2)) to obtain a reactive silyl group-containingpolyether polymer.

The reactive silyl group-containing polyether polymer (B) preferably hasa molecular weight distribution (Mw/Mn) of 1.6 or less, more preferably1.5 or less, and particularly preferably 1.4 or less.

One of reactive silyl group-containing polyether polymers (B) may beused alone, or two or more of these may be used in combination.

With respect to the number average molecular weight of the reactivesilyl group-containing polyether polymer (B), the lower limit ispreferably 3,000 or higher, more preferably 5,000 or higher, andparticularly preferably 8,000 or higher, and the upper limit ispreferably 100,000 or less, more preferably 50,000 or less, andparticularly preferably 35,000 or less, as determined by GPC on thepolystyrene equivalent basis. If the number average molecular weight isless than 3,000, the resulting cured product is likely to have lowerelongation at break. If the number average molecular weight exceeds100,000, the curing rate is likely to be reduced due to too low aconcentration of reactive silyl groups. In addition, the reactive silylgroup-containing polyether polymer (B) is likely to be difficult tohandle due to too high viscosity.

When the molecular weights are compared between the reactive silylgroup-containing polyether polymer (A) and the reactive silylgroup-containing polyether polymer (B), the molecular weight of thepolymer (A) is preferably larger than that of the polymer (B). Thepolymer (A) reacts in the initial stage of curing and is thusresponsible for tack development. In this regard, the polymer (A) havinga higher molecular weight is preferred because it is likely to causehigher rate of tack development and also offer higher tack strength. Onthe other hand, the polymer (B) decreases the viscosity of thecomposition while it is cured later than the polymer (A) and is thusresponsible for enhancing the final strength of the adhesive. Hence, themolecular weight of the polymer (B) needs to be lower than that of thepolymer (A) and its number average molecular weight is preferablysmaller by 5000 or higher.

The reactive silyl group-containing polyether polymer (B) is mostpreferably a mixture of a polymer (b1) having a molecular weight of 8000or higher and a polymer (b2) having a molecular weight less than 8000because the resulting composition is likely to be excellent in thebalance between the viscosity before curing and the physical propertiesafter curing (i.e., higher elongation and strength of the curedproduct). In the case of using the polymer (b1) having a molecularweight of 8000 or higher and the polymer (b2) having a molecular weightless than 8000, the number average molecular weight of the polymer (B)is defined as an apparent number average molecular weight calculatedbased on the mixture of the polymer (b1) and the polymer (b2) regardedas one polymer.

The reactive silyl group introduction rate (silylation rate) of thereactive silyl group-containing polyether polymer (B) is, on average permolecule, more than 50%, more preferably 60% or more, and particularlypreferably 60 to 85%, of all molecular terminal groups in order toprovide a favorable rubbery cured product. If the number of reactivesilyl groups accounts for less than 50% of all molecular terminalgroups, the curability may be insufficient, which makes it difficult toprovide a favorable rubber elastic behavior. The number of reactivesilyl groups per molecule is preferably 1 to 7, more preferably 1 to3.4, and particularly preferably 1 to 2.6, on average.

The backbone structure of the reactive silyl group-containing polyetherpolymer (B) is preferably a linear structure or a branched structurehaving 1 to 6 branches, and is more preferably a linear structure or abranched structure having 1 to 2 branches, and particularly preferably alinear structure or a branched structure having 1 branch. If the numberof terminals bonded to the reactive silyl group per molecule isincreased, the crosslink density may be increased, which makes itdifficult to offer favorable elongation properties.

The reactive silyl group may be located at a backbone terminal, or at aside chain terminal, or at both terminals, of the organic polymer chain.In particular, the reactive silyl group is preferably located at abackbone terminal of the molecular chain because the molecular weightbetween crosslinks is then increased, which tends to provide a rubberycured product having higher strength, higher elongation, and lowerelastic modulus.

The blend ratio of the reactive silyl group-containing polyether polymer(B) is not particularly limited. In applications such as sealingmaterials and adhesives, relative to 100 parts by weight of the polymer(A), the lower limit is preferably 10 parts by weight or higher, morepreferably 100 parts by weight or higher, and particularly preferably150 parts by weight or higher, and the upper limit is preferably 1000parts by weight or less, more preferably 950 parts by weight or less,still more preferably 900 parts by weight or less, even more preferably700 parts by weight or less, and particularly preferably 400 parts byweight or less.

Alternatively, in application to contact adhesives, relative to 100parts by weight of the polymer (A), the lower limit is preferably 100parts by weight or higher, and more preferably 150 parts by weight orhigher, and the upper limit is preferably 900 parts by weight or less,more preferably 600 parts by weight or less, and particularly preferably500 parts by weight or less. An adhesive with a higher proportion of thereactive silyl group-containing polyether polymer (A) is likely to fallinto a so-called skinning (the surface of the adhesive is cured duringthe course of curing) and thus the working life tends to be short. Ifthe ratio of the polymer (B) is less than 5 parts by weight, the curingis likely to be slowed.

(Reactive Silyl Group-containing (Meth)Acrylic Polymer (C))

The reactive silyl group-containing (meth)acrylic polymer (C) in thepresent invention is not particularly limited as long as it is a(meth)acrylic polymer having a reactive silyl group represented byformula (3) at a molecular chain terminal and/or a side chain:—Z—(CH₂)_(n)—SiR¹ _(a)R² _(b)X_(c)   (3)

wherein R¹, R², and X are defined as mentioned in formula (1); Zrepresents a linking group selected from —CO—O—, —O—CO—N(R⁹)—,—N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁹is defined as mentioned in formula (1); n represents a number of 1 to 8;a is 0, 1, or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided thata+b+c=3 is satisfied; and in the case that a plurality of R¹s, R²s, orXs exist, they may be the same as or different from each other.

(Regarding Reactive Silyl Group of Formula (3))

The polymer end of the reactive silyl group-containing (meth)acrylicpolymer (C) is required to be bonded to the silicon atom in the reactivesilyl via the linking group represented by —Z—(CH₂)_(n)—. Such areactive silyl group-containing (meth)acrylic organic polymer (C) in thepresent invention in which a specific linking group is introduced can beaffected by the number of carbon atoms between the silicon atom in thereactive silyl group and Z in terms of curing rate and provides rapidcurability with n being 1.

Specific examples of the structure of the group represented by —SiR¹_(a)R² _(b)X_(c) in formula (3) include a(chloromethyl)methoxymethylsilyl group, a bis(chloromethyl)methoxysilylgroup, a (chloromethyl)dimethoxysilyl group, a(1-chloroethyl)dimethoxysilyl group, a (chloromethyl)diethoxysilylgroup, a (dichloromethyl)dimethoxysilyl group, a(1-chloropropyl)dimethoxysilyl group, a (methoxymethyl)dimethoxysilylgroup, a (methoxymethyl)diethoxysilyl group, a(ethoxymethyl)dimethoxysilyl group, an (aminomethyl)dimethoxysilylgroup, an (dimethylaminomethyl)dimethoxysilyl group, a(diethylaminomethyl)dimethoxysilyl group, a(diethylaminomethyl)diethoxysilyl group, an(N-(2-aminoethyl)aminomethyl)dimethoxysilyl group, a(1-aminopropyl)dimethoxysilyl group, a(1-(N-methylamino)propyl)dimethoxysilyl group, a(1-(N,N-dimethylamino)propyl)dimethoxysilyl group, a(3-(2-aminoethyl)aminopropyl)dimethoxysilyl group, a(3,3,3-trifluoropropyl)dimethoxysilyl group, an(acetoxymethyl)dimethoxysilyl group, an (acetoxymethyl)diethoxysilylgroup, a methyldimethoxysilyl group, a methyldiethoxysilyl group, amethyldiisopropoxysilyl group, a trimethoxysilyl group, a triethoxysilylgroup, a triisopropoxysilyl group, a methoxydimethylsilyl group, and anethoxydimethylsilyl group. More preferred among these are amethyldimethoxysilyl group, a methyldiethoxysilyl group, atrimethoxysilyl group, and a triethoxysilyl group, in terms of theavailability of the starting material silane compound.

(Regarding Backbone Structure of Reactive Silyl Group-containing(Meth)Acrylic Polymer (C))

The monomer units constituting the backbone structure of the reactivesilyl group-containing (meth)acrylic polymer (C) in the presentinvention are not particularly limited, and one kind and/or two or morekinds of monomer (c) having a (meth)acrylic structure are preferablyused.

Specific examples of the monomer (c) having a (meth)acrylic structureinclude: alkyl(meth)acrylate monomers such as methyl(meth)acrylate,ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate,n-butyl(meth)acrylate, isobutyl (meth)acrylate, s-butyl(meth)acrylate,tert-butyl (meth)acrylate, neopentyl(meth)acrylate, n-hexy(meth)acrylate, n-heptyl(meth)acrylate, 2-ethylhexyl (meth)acrylate,nonyl(meth)acrylate, decyl(meth)acrylate, undecyl (meth)acrylate,lauryl(meth)acrylate, tridecyl (meth)acrylate, tetradecyl(meth)acrylate,hexadecyl (meth)acrylate, stearyl(meth)acrylate, behenyl (meth)acrylate,and cyclohexyl(meth)acrylate; and (meth)acrylate monomers such as2-methoxyethyl (meth)acrylate, 3-methoxybutyl(meth)acrylate,2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, ethyleneoxide adducts of (meth)acrylic acid, 2,2,2-trifluoroethyl(meth)acrylate,3,3,3-trifluoropropyl(meth)acrylate,3,3,4,4,4-pentafluorobutyl(meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl(meth)acrylate,trifluoromethyl(meth)acrylate, perfluoroethyl (meth)acrylate,bis(trifluoromethyl)methyl(meth)acrylate,2-trifluoromethyl-2-perfluoroethylethyl(meth)acrylate,2-perfluorohexylethyl(meth)acrylate, 2-perfluorodecylethyl(meth)acrylate, 2-perfluorohexadecylethyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, chloroethyl (meth)acrylate,tetrahydrofurfuryl(meth)acrylate, and glycidyl(meth)acrylate. One ofthese monomers may be used alone, or two or more of these may be used incombination.

A monomer copolymerizable with such a monomer may also be used to theextent that does not impair the physical properties. Examples of suchmonomers include: styrene monomers such as styrene, vinyltoluene,α-methylstyrene, chlorostyrene, and styrenesulfonic acid;fluorine-containing vinyl monomers such as perfluoroethylene,perfluoropropylene, and vinylidene fluoride; maleic acid and itsderivatives such as maleic acid, maleic anhydride, and monoalkyl ordialkyl esters of maleic acid; fumaric acid and its derivatives such asfumaric acid and monoalkyl or dialkyl esters of fumaric acid; maleimidemonomers such as maleimide, methylmaleimide, ethylmaleimide,propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide,dodecylmaleimide, stearylmaleimide, phenylmaleimide, andcyclohexylmaleimide; vinyl ester monomers such as vinyl acetate, vinylpropionate, vinyl pivalate, vinyl benzoate, and vinyl cinnamate; olefinmonomers such as ethylene and propylene; conjugated diene monomers suchas butadiene and isoprene; (meth)acrylamide; (meth)acrylonitrile; andvinyl monomers such as vinyl chloride, vinylidene chloride, allylchloride, allyl alcohol, ethyl vinyl ether, and butyl vinyl ether. Oneof these monomers may be used alone, or two or more of these may be usedin combination.

The monomer units constituting the backbone structure of the reactivesilyl group-containing (meth)acrylic polymer (C) preferably contain 50%by weight or more, more preferably 70% by weight or more, ofalkyl(meth)acrylate monomer in terms of the compatibility with thereactive silyl group-containing polyether polymer (A). Thealkyl(meth)acrylate monomer is preferably a combination of analkyl(meth)acrylate monomer (c1) containing a C1 to C8 alkyl group andan alkyl(meth)acrylate monomer (c2) containing a C10 to C30 alkyl group.In this case, the ratio between the alkyl(meth)acrylate monomer (c1) andthe alkyl(meth)acrylate monomer (c2) is preferably (c1):(c2)=95:5 to40:60, and more preferably 90:10 to 60:40, by weight ratio.

As combinations without the use of the component (c2), for example, acombination of methyl(meth)acrylate, butyl (meth)acrylate, and analkyl(meth)acrylate monomer containing a C7 to C9 alkyl group, acombination of an alkyl (meth)acrylate monomer containing a C1 or C2alkyl group and an alkyl(meth)acrylate monomer containing a C7 to C9alkyl group, and other combinations are preferred in terms of thecompatibility with the reactive silyl group-containing polyether polymer(A).

The reactive silyl group-containing (meth)acrylic polymer (C) can beobtained by various polymerization methods. Its production method is notparticularly limited, and radical polymerization is preferred in termsof versatile monomers and easy control.

Radical polymerization methods can be classified into “general radicalpolymerization” and “controlled radical polymerization”. The “generalradical polymerization” is a convenient polymerization method whichmerely involves polymerization using a polymerization initiator such asan azo compound or peroxide. On the other hand, the “controlled radicalpolymerization” is a method capable of introducing a specific functionalgroup into a controlled site such as a terminal. The “controlled radicalpolymerization” methods can be further classified into “chain transferagent polymerization” and “living radical polymerization”. The “chaintransfer agent polymerization” is characterized by polymerization usinga chain transfer agent containing a specific functional group andproduces a vinyl polymer containing the functional group at a terminal.On the other hand, the “living radical polymerization” is characterizedin that a growing polymer end grows without side reactions such astermination, and this method produces a polymer having a molecularweight nearly as high as designed. In the present invention, any ofthese polymerization methods may be used.

Specific examples of the “general radical polymerization” includesolution polymerization and bulk polymerization, which involve adding apolymerization initiator, a chain transfer agent, a solvent, etc.,followed by polymerization at 50 to 150° C.

Examples of the polymerization initiator include: azo compounds such as2,2′-azobis(2-methylbutyronitrile), dimethyl2,2′-azobis(2-methylpropionate), 2,2′-azobis(2,4-dimethylvaleronitrile),2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile),2,2′-azobis[N-(2-propenyl)-2-methylpropionamide], and1,1′-azobis(cyclohexane-1-carbonitrile); diacyl peroxides such asbenzoyl peroxide, isobutyryl peroxide, isononanoyl peroxide, decanoylperoxide, lauroyl peroxide, p-chlorobenzoyl peroxide, anddi(3,5,5-trimethylhexanoyl)peroxide; peroxydicarbonates such asdiisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate,di-2-ethylhexyl peroxydicarbonate, di-1-methylheptyl peroxydicarbonate,di-3-methoxybutyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate;peroxy esters such as tert-butyl perbenzoate, tert-butyl peracetate,tert-butyl per-2-ethylhexanoate, tert-butyl perisobutyrate, tert-butylperpivalate, tert-butyl diperadipate, and cumyl perneodecanoate; ketoneperoxides such as methyl ethyl ketone peroxide and cyclohexanoneperoxide; dialkyl peroxides such as di-tert-butyl peroxide, dicumylperoxide, tert-butylcumyl peroxide, and1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane; hydroperoxides suchas cumene hydroxyperoxide and tert-butyl hydroperoxide; and peroxidessuch as 1,1-di(tert-hexylperoxy)-3,3,5-trimethylcyclohexane. One ofthese polymerization initiators may be used alone, or two or more ofthese may be used in combination.

Examples of the chain transfer agent include mercapto group-containingcompounds such as n-dodecylmercaptan, tert-dodecylmercaptan, andlaurylmercaptan. In order to introduce a reactive silyl group into themolecular chain terminal of the (meth)acrylic polymer, for example, acompound (c3) containing a reactive silyl group and a mercapto group ispreferably used, such as 3-mercaptopropyltrimethoxysilane,3-mercaptopropylmethyldimethoxysilane, mercaptomethyltrimethoxysilane,mercaptomethylmethyldimethoxysilane,3-mercaptopropylchloromethyldimethoxysilane,3-mercaptopropylmethoxymethyldimethoxysilane,3-mercaptopropylaminomethyldimethoxysilane, and3-mercaptopropyl-N,N-dimethylaminomethyldimethoxysilane. One of thesechain transfer agents may be used alone, or two or more of these may beused in combination.

Examples of the solvent include: aromatic compounds such as toluene,xylene, styrene, ethylbenzene, p-dichlorobenzene, di-2-ethylhexylphthalate, and di-n-butyl phthalate; hydrocarbon compounds such ashexane, heptane, octane, cyclohexane, and methylcyclohexane; carboxylatecompounds such as butyl acetate, n-propyl acetate, and isopropylacetate; ketone compounds such as methyl isobutyl ketone and methylethyl ketone; dialkyl carbonate compounds such as dimethyl carbonate anddiethyl carbonate; and alcohol compounds such as n-propanol, 2-propanol,n-butanol, 2-butanol, isobutanol, tert-butanol, and amyl alcohol. Amongthese, one or more selected from dialkyl carbonate compounds and alcoholcompounds are preferred in terms of exclusion from substances specifiedby the Ministry of Health, Labor and Welfare's concentration guidelines,odor, environmental load, etc. In terms of boiling point and ofreduction in the emission of total volatile organic compounds from thecomposition, measured by the method described in the Feb. 14, 2001edition of GEV Specification and Classification Criteria established byGEV (Gemeinschaft Emissionskontrollierte Verlegewerkstoffe e.V.), morepreferred are dimethyl carbonate, n-propanol, 2-propanol, n-butanol,2-butanol, isobutanol, and tert-butanol, and particularly preferred are2-propanol and isobutanol.

In addition to the solvent, a reactive silyl group-containing polyetherpolymer or its precursor compound, a plasticizer described later, etc.,may also be used in the polymerization.

The “chain transfer agent polymerization” is a method that canquantitatively introduce a functional group into a polymer end, comparedwith the “general radical polymerization”.

Unlike the polymerization method mentioned above, the “living radicalpolymerization” is a method that can produce a polymer having a desiredmolecular weight, a narrow molecular weight distribution, and lowviscosity and can also introduce a monomer containing a specificfunctional group into almost any site in a polymer. In a narrow sense,living polymerization refers to polymerization in which a molecularchain grows with its terminal kept active constantly. In general, theliving polymerization also encompasses pseudo-living polymerization inwhich a molecular chain grows with its terminal in equilibrium betweeninactive and active states.

Examples of the “living radical polymerization” include a method using acobalt-porphyrin complex as described in J. Am. Chem. Soc., 1994, vol.116, p. 7943, a method using a nitroxide radical as described in JP-T2003-500378, and atom transfer radical polymerization (ATRP) using aninitiator such as an organic halide or a sulfonyl halide compound and atransition metal complex catalyst as described in JP-A H11-130931. Theatom transfer radical polymerization as used herein also encompassesso-called reverse atom transfer radical polymerization as described inMacromolecules, 1999, vol. 32, p. 2872, i.e., a polymerization methodwhich creates a high oxidation state as obtained when radicals aregenerated by a common atom transfer radical polymerization catalyst, forexample, a polymerization method that creates the same equilibrium as inatom transfer radical polymerization, as a result of the action of anordinary radical initiator such as peroxide on Cu(II′) derived fromCu(I) as a catalyst.

In addition to these polymerization methods, other methods may be used,including: a method which involves using a metallocene catalyst and athiol compound having at least one reactive silyl group per molecule toproduce an acrylic polymer, as described in JP-A 2001-040037; and ahigh-temperature continuous polymerization method which involvescontinuously polymerizing a vinyl monomer using a stirred tank reactor,as described in JP-T S57-502171, JP-A S59-006207, and JP-A S60-511992.

(Regarding Method for Producing Reactive Silyl Group-containing(Meth)Acrylic Polymer (C))

The method for introducing a reactive silyl group into a (meth)acrylicpolymer is not particularly limited and may be, for example, any of thefollowing methods (i) to (iv):

(i) a compound (c4) containing a polymerizable unsaturated group and areactive silyl group is copolymerized with a monomer (b) having the(meth)acrylic structure mentioned above;

(ii) a monomer (c) having the (meth)acrylic structure is copolymerizedin the presence of the compound (c3) containing a reactive silyl groupand a mercapto group as a chain transfer agent;

(iii) a compound containing a polymerizable unsaturated group and areactive functional group (e.g., acrylic acid, 2-hydroxyethyl acrylate)is copolymerized with a monomer (b) having the (meth)acrylic structure,and the resulting product is then reacted with a compound containing areactive silyl group and a functional group that is reactive with thereactive functional group (e.g., isocyanatosilane compounds); and

(iv) a monomer (c) having the (meth)acrylic structure is polymerized byliving radical polymerization, and a reactive silyl group is thenintroduced into the molecular chain terminal of the resulting polymer.

These methods may be used in any combination.

Of these methods, a combination of the methods (i) and (ii) is morepreferably used because it can introduce a reactive silyl group into amolecular chain terminal or a side chain, or both. The method (iv) ismore preferred because it can produce a polymer having a desiredmolecular weight, a narrow molecular weight distribution, and lowviscosity.

Examples of the compound (c4) containing a polymerizable unsaturatedgroup and a reactive silyl group include: compounds containing a(meth)acryloxy group and a reactive silyl group, such as3-(meth)acryloxypropyltrimethoxysilane,3-(meth)acryloxypropylmethyldimethoxysilane,3-(meth)acryloxypropyltriethoxysilane,((meth)acryloxymethyl)trimethoxysilane,((meth)acryloxymethyl)methyldimethoxysilane,(meth)acryloxymethyldimethylmethoxysilane,3-(meth)acryloxypropylchloromethyldimethoxysilane,3-(meth)acryloxypropylmethoxymethyldimethoxysilane,3-(meth)acryloxypropylaminomethyldimethoxysilane, and 3-(meth)acryloxypropyl-N,N-dimethylaminomethyldimethoxysilane; andcompounds containing a vinyl group and a reactive silyl group, such asvinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane,vinylchloromethyldimethoxysilane, vinylmethoxymethyldimethoxysilane,vinylaminomethyldimethoxysilane, andvinyl-N,N-dimethylaminomethyldimethoxysilane. One of these compounds maybe used alone, or two or more of these may be used in combination.

The number average molecular weight of the reactive silylgroup-containing (meth)acrylic polymer (C) in the present invention isnot particularly limited, and the lower limit is preferably 500 orhigher, and more preferably 1,000 or higher, and the upper limit ispreferably 100,000 or less, more preferably 50,000 or less, andparticularly preferably 30,000 or less, as determined by GPC on thepolystyrene equivalent basis.

The reactive silyl group of the reactive silyl group-containing(meth)acrylic polymer (C) in the present invention may be introduced atany of a molecular chain terminal and a side chain. In terms ofadhesion, the reactive silyl group is preferably introduced at both amolecular chain terminal and a side chain. With respect to the number ofreactive silyl groups on average per molecule, the lower limit ispreferably 0.5 or more, more preferably 0.7 or more, and particularlypreferably 1.0 or more, and the upper limit is preferably 2.0 or less,more preferably 1.9 or less, and particularly preferably 1.8 or less.

The blend ratio of the reactive silyl group-containing (meth)acrylicpolymer (C) is not particularly limited. In application to sealingmaterials and adhesives, relative to 100 parts by weight of the reactivesilyl group-containing polyether polymer (A), the lower limit ispreferably 10 parts by weight or higher, more preferably 20 parts byweight or higher, and particularly preferably 40 parts by weight orhigher, and the upper limit is preferably 700 parts by weight or less,more preferably 500 parts by weight or less, and particularly preferably30 parts by weight or less. If the ratio of the polymer (C) is less than10 parts by weight, sufficient effect on initial tack or tensileproperties may not be obtained. If the ratio of the polymer (C) exceeds700 parts by weight, the resulting composition is likely to be difficultto handle due to too high viscosity.

Alternatively, in application to contact adhesives, relative to 100parts by weight in total of the polymer (A) and the polymer (B), thelower limit is preferably 5 parts by weight or higher, and morepreferably 10 parts by weight or higher, and the upper limit ispreferably 200 parts by weight or less, and more preferably 100 parts byweight or less.

In order to secure the initial tack properties of contact adhesives, thecurable composition of the present invention preferably contains thereactive silyl group-containing polyether polymer (A), the reactivesilyl group-containing polyether polymer (B), and the reactive silylgroup-containing (meth)acrylic polymer (C).

The curable composition of the present invention may further contain acondensation catalyst (D) for the purpose of promoting the cross-linkingreaction of the reactive silyl groups in the reactive silylgroup-containing polyether polymer (A), and the reactive silylgroup-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer (C) via hydrolysis andcondensation.

Examples of the condensation catalyst include, but not limited to,conventionally known catalysts. In particular, amine compounds andcarboxylic acids are preferred because they cause the polyether polymer(A) containing the reactive silyl group represented by formula (1) to becured in a very short time.

Examples of amine compounds (d1) that can be used as the condensationcatalyst include, but not limited to: aliphatic primary amines such asmethylamine, ethylamine, propylamine, isopropylamine, butylamine,amylamine, hexylamine, octylamine, 2-ethylhexylamine, nonylamine,decylamine, laurylamine, pentadecylamine, cetylamine, stearylamine, andcyclohexylamine; aliphatic secondary amines such as dimethylamine,diethylamine, dipropylamine, diisopropylamine, dibutylamine,diamylamine, dihexylamine, dioctylamine, di(2-ethylhexyl)amine,didecylamine, dilaurylamine, dicetylamine, distearylamine,methylstearylamine, ethylstearylamine, and butylstearylamine; aliphatictertiary amines such as triamylamine, trihexylamine, and trioctylamine;aliphatic unsaturated amines such as triallylamine and oleylamine;aromatic amines such as aniline, laurylaniline, stearylaniline, andtriphenylamine; nitrogen-containing heterocyclic compounds such aspyridine, 2-aminopyridine, 2-(dimethylamino)pyridine,4-(dimethylaminopyridine), 2-hydroxypyridine, imidazole,2-ethyl-4-methylimidazole, morpholine, N-methylmorpholine, piperidine,2-piperidinemethanol, 2-(2-piperidino)ethanol, piperidone,1,2-dimethyl-1,4,5,6-tetrahydropyrimidine,1,8-diazabicyclo(5,4,0)undecene-7 (DBU),6-(dibutylamino)-1,8-diazabicyclo(5,4,0)undecene-7 (DBA-DBU),1,5-diazabicyclo(4,3,0)nonene-5 (DBN), 1,4-diazabicyclo(2,2,2)octane(DABCO), and aziridine, as well as other amines including amines such asmonoethanolamine, diethanolamine, triethanolamine, 3-hydroxypropylamine,ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-1,3-propanediamine, N,N′-dimethyl-1,3-propanediamine,diethylenetriamine, triethylenetetramine, 2-(2-aminoethylamino)ethanol,benzylamine, 3-methoxypropylamine, 3-lauryloxypropylamine,3-dimethylaminopropylamine, 3-diethylaminopropylamine,3-dibutylaminopropylamine, 3-morpholinopropylamine,2-(1-piperazinyl)ethylamine, xylylenediamine, and2,4,6-tris(dimethylaminomethyl)phenol; guanidines such as guanidine,phenylguanidine, and diphenylguanidine; and biguanides such asbutylbiguanide, 1-o-tolylbiguanide, and 1-phenylbiguanide.

Preferred among these are amidines such as1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU, DBA-DBU, and DBN;guanidines such as guanidine, phenylguanidine, and diphenylguanidine;and biguanides such as butylbiguanide, 1-o-tolylbiguanide, and1-phenylbiguanide, in terms of high activity. Also preferred arearyl-substituted biguanides such as 1-o-tolylbiguanide and1-phenylbiguanide, because high adhesion can then be expected.

Amine compounds are basic. Amine compounds whose conjugate acids have apKa value of 11 or larger have high catalytic activity and are thuspreferred. For example, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, DBU,DBN and the like, whose conjugate acids have a pKa value of 12 orlarger, have high catalytic activity and are thus particularlypreferred.

In the present invention, an amino group-containing silane couplingagent (hereinafter referred to also as aminosilane) may be used as theamine compound serving as the condensation catalyst. The aminosilanerefers to a compound that contains a group containing a hydrolyzablegroup bonded to a silicon atom (hereinafter referred to also ashydrolyzable silyl group) and a substituted or unsubstituted aminogroup.

Examples of the substituent in the substituted amino group include, butnot limited to, alkyl groups, aralkyl groups, and aryl groups.

The hydrolyzable silyl group is not particularly limited, and may be,for example, a hydrogen atom, a halogen atom, an alkoxy group, anaryloxy group, an alkenyloxy group, an acyloxy group, a ketoxymategroup, an amino group, an amido group, an acid amido group, an aminooxygroup, a mercapto group or the like. Preferred among these are a halogenatom, an alkoxy group, an alkenyloxy group, and an aryloxy group, interms of high activity. A chlorine atom or an alkoxy group can beintroduced easily and is thus preferred. In terms of mild hydrolysis andeasy workability, more preferred are alkoxy groups such as a methoxygroup and an ethoxy group, and particularly preferred are a methoxygroup and an ethoxy group. Also, an ethoxy group and an isopropenoxygroup are preferred in terms of safety because compounds eliminated byreaction are ethanol and acetone, respectively. The number ofhydrolyzable groups bonded to a silicon atom in the aminosilane ispreferably 2 or more, particularly 3 or more.

Examples of the aminosilane include, but not limited to,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane,N-β-aminoethyl-γ-aminopropyltrimethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane,N-β-aminoethyl-γ-aminopropyltriethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane,N-β-aminoethyl-γ-aminopropyltriisopropoxysilane,N-β-(β-aminoethyl)aminoethyl-γ-aminopropyltrimethoxysilane,N-6-aminohexyl-γ-aminopropyltrimethoxysilane,3-(N-ethylamino)-2-methylpropyltrimethoxysilane,γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane,N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane,N-vinylbenzyl-γ-aminopropyltriethoxysilane,N-cyclohexylaminomethyltriethoxysilane,N-cyclohexylaminomethyldiethoxymethylsilane,N-phenylaminomethyltrimethoxysilane,(2-aminoethyl)aminomethyltrimethoxysilane, andN,N′-bis[3-(trimethoxysilyl)propyl]ethylenediamine.

Among these aminosilanes, aminosilanes containing an amino group (—NH₂)are preferred in terms of curability; and preferred areγ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, andN-β-aminoethyl-γ-aminopropyltrimethoxysilane, in terms of theiravailability.

A ketimine compound that is hydrolyzed into the amine compound can alsobe used as the condensation catalyst.

Examples of usable condensation catalysts other than the amine compoundsinclude: carboxylic acids such as 2-ethylhexanoic acid, octylic acid,neodecanoic acid, oleic acid, and naphthenic acid; metal salts ofcarboxylic acids such as tin carboxylates, lead carboxylates, bismuthcarboxylates, potassium carboxylates, calcium carboxylates, bariumcarboxylates, titanium carboxylates, zirconium carboxylates, hafniumcarboxylates, vanadium carboxylates, manganese carboxylates, ironcarboxylates, cobalt carboxylates, nickel carboxylates, and ceriumcarboxylates; titanium compounds such as tetrabutyl titanate,tetrapropyl titanate, tetrakis(acetylacetonato)titanium,bis(acetylacetonato)diisopropoxytitanium, and diisopropoxybis(ethylacetoacetato)titanium; dibutyltin compounds such as dibutyltindilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltindioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltinbis(methylmaleate), dibutyltin bis(ethylmaleate), dibutyltinbis(butylmaleate), dibutyltin bis(octylmaleate), dibutyltinbis(tridecylmaleate), dibutyltin bis(benzylmaleate), dibutyltindiacetate, dibutyltin dimethoxide, dibutyltin bis(nonylphenoxide),dibutenyltin oxide, dibutyltin oxide, dibutyltin bis(acetylacetonate),dibutyltin bis(ethylacetoacetonate), reaction products of dibutyltinoxide and a silicate compound, and reaction products of dibutyltin oxideand a phthalic acid ester; dioctyltin compounds such as dioctyltinbis(triethoxysilicate), dioctyltin dimethoxide, dioctyltindiacetylacetonate, dioctyltin diacetate, dioctyltin dioctoate,dioctyltin diversatate, dioctyltin dilaurate, dioctyltin distearate,dioctyltin dibehenate, dioctyltin dioleate, bis(dioctyltin acetate)oxide, bis(dioctyltin octoate) oxide, bis(dioctyltin versatate) oxide,bis(dioctyltin laurate) oxide, bis(dioctyltin stearate) oxide,bis(dioctyltin behenate) oxide, dioctyltin bis(ethylmaleate), dioctyltinbis (octylmaleate), and dioctyltin bisisooctylthioglycolate; aluminumcompounds such as tris(acetylacetonato)aluminum,tris(ethylacetoacetato)aluminum, and diisopropoxyaluminumethylacetoacetate; zirconium compounds such astetrakis(acetylacetonato)zirconium; and various metal alkoxide compoundssuch as tetrabutoxyhafnium; acidic organophosphoric acid esters; organicsulfonic acids such as trifluoromethanesulfonic acid; inorganic acidssuch as hydrochloric acid, phosphoric acid, and boronic acid.

Preferred among these condensation catalysts are amine compounds,carboxylic acids, and dioctyltin compounds, and more preferred are aminecompounds, in terms of curability and environmental load.

Two or more different catalysts may be used in combination as thecondensation catalyst. For example, a combination of an amine compoundand an organotin compound (dibutyltin compound or dioctyltin compound)is preferably used because of the possible effect of enhancing thecurability.

The amount of condensation catalyst used is preferably 0.001 to 20 partsby weight, more preferably 0.01 to 15 parts by weight, and particularlypreferably 0.01 to 10 parts by weight, for each 100 parts by weight ofthe reactive silyl group-containing polyether polymer (A). If the amountof condensation catalyst is less than 0.001 parts by weight, the curingrate may be insufficient, which may make it difficult to allow thecuring reaction to proceed sufficiently. Conversely, if the amount ofcondensation catalyst exceeds 20 parts by weight, the working life ofthe curable composition is likely to be shortened due to too rapid acuring rate and thus the workability tends to be poor; moreover, thestorage stability tends to be poor.

The curable composition of the present invention may optionally containa plasticizer, an adhesion-imparting agent, a filler, aphysical-property modifier, an anti-sagging agent (thixotropy-impartingagent), a stabilizer, etc.

The curable composition of the present invention may contain aplasticizer. Addition of a plasticizer enables to adjust the viscosityand slump properties of the curable composition, and the mechanicalproperties such as tensile strength and elongation of a cured productobtained by curing the curable composition. Specific examples of theplasticizer include: phthalate compounds such as dibutyl phthalate,diisononyl phthalate (DINP), diheptyl phthalate, di(2-ethylhexyl)phthalate, diisodecyl phthalate (DIDP), and butyl benzyl phthalate;terephthalate compounds such as bis(2-ethylhexyl)-1,4-benzenedicarboxylate (specifically, product name: EASTMAN 168 (product ofEastman Chemical Company)); non-phthalate compounds such as1,2-cyclohexanedicarboxylic acid diisononyl ester (specifically, productname: Hexamoll DINCH (product of BASF)); aliphatic polycarboxylatecompounds such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate,diisodecyl succinate, and tributyl acetylcitrate; unsaturated fatty acidester compounds such as butyl oleate and methyl acetylricinoleate;alkylsulfonic acid phenyl esters (specifically, product name: Mesamoll(product of Lanxess)); phosphate compounds such as tricresyl phosphateand tributyl phosphate; trimellitate compounds; chlorinated paraffins;hydrocarbon oils such as alkyldiphenyls and partially hydrogenatedterphenyls; process oils; and epoxy plasticizers such as epoxidizedsoybean oil and benzyl epoxystearate.

Also, polymer plasticizers may be used. In the case of using a polymerplasticizer, the initial physical properties can be maintained for along period of time, compared with the case of using alow-molecular-weight plasticizer which is a plasticizer containing nopolymer moiety in the molecule. The drying properties (coatingproperties) of an alkyd coating material applied to the resulting curedproduct can also be improved. Specific examples of the polymerplasticizer include, but not limited to, vinyl polymers obtained bypolymerizing vinyl monomers by various methods; esters of polyalkyleneglycols, such as diethylene glycol dibenzoate, triethylene glycoldibenzoate, and pentaerythritol esters; polyester plasticizers obtainedfrom dibasic acids (e.g., sebacic acid, adipic acid, azelaic acid,phthalic acid) and divalent alcohols (e.g., ethylene glycol, diethyleneglycol, triethylene glycol, propylene glycol, dipropylene glycol);polyethers such as polyether polyols with a number average molecularweight of 500 or higher, or even 1000 or higher (e.g., polyethyleneglycol, polypropylene glycol, polytetramethylene glycol) and theirderivatives obtained by replacing the hydroxy group of these polyetherpolyols with an ester group, ether group or the like; polystyrenes suchas polystyrene and poly-α-methylstyrene; polybutadiene, polybutene,polyisobutylene, polybutadiene-acrylonitrile, and polychloroprene.

Preferred among these polymer plasticizers are ones compatible with thereactive silyl group-containing polyether polymer (A), and the reactivesilyl group-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer (C). In this respect, polyethersand vinyl polymers are preferred. Use of polyethers as plasticizers ispreferred because the surface curability and depth curability are thenimproved and curing retardation will not occur after storage. Amongthese, polypropyrene glycol is more preferred. In terms ofcompatibility, weather resistance, and heat resistance, vinyl polymersare preferred. Among vinyl polymers, acrylic polymers and/or methacrylicpolymers are preferred, and acrylic polymers such as polyalkyl acrylatesare more preferred. The polymers may preferably be synthesized by livingradical polymerization, more preferably by atom transfer radicalpolymerization, because these methods allow production of polymershaving a narrow molecular weight distribution and low viscosity. Alsopreferred are polymers produced by the so-called SGO process in whichalkyl acrylate monomers are continuously bulk-polymerized underhigh-temperature and high-pressure conditions, as disclosed in JP-A2001-207157.

The number average molecular weight of the polymer plasticizer ispreferably 500 to 15,000, more preferably 800 to 10,000, still morepreferably 1,000 to 8,000, particularly preferably 1,000 to 5,000, andmost preferably 1,000 to 3,000. If the molecular weight is too low, theplasticizer exudes due to heat or rain over time and therefore theinitial physical properties cannot be maintained for a long period oftime. If the molecular weight is too high, the viscosity becomes highand the workability is thus deteriorated.

The molecular weight distribution of the polymer plasticizer is notparticularly limited, and is preferably narrow; the molecular weightdistribution is preferably less than 1.80, more preferably 1.70 or less,still more preferably 1.60 or less, even more preferably 1.50 or less,particularly preferably 1.40 or less, and most preferably 1.30 or less.

The number average molecular weight of the polymer plasticizer ismeasured by the GPC method in the case of a vinyl polymer, or byterminal group analysis in the case of a polyether polymer. Also, themolecular weight distribution (Mw/Mn) is measured by the GPC method (onthe polystyrene equivalent basis).

The polymer plasticizer may or may not contain a reactive silyl group.If the polymer plasticizer contains a reactive silyl group, the polymerplasticizer functions as a reactive plasticizer, so that transfer of theplasticizer from the cured product can be prevented. If the polymerplasticizer contains a reactive silyl group, the number of reactivesilyl groups is preferably 1 or less, and more preferably 0.8 or less,on average per molecule. In the case of using a reactive silylgroup-containing plasticizer, particularly a reactive silylgroup-containing polyether polymer, the number average molecular weightthereof needs to be lower than that of the reactive silylgroup-containing polyether polymer (A).

The amount of plasticizer is 5 to 150 parts by weight, preferably 10 to120 parts by weight, and more preferably 20 to 100 parts by weight, foreach 100 parts by weight in total of the reactive silyl group-containingpolyether polymer (A), and the reactive silyl group-containing polyetherpolymer (B) and/or the reactive silyl group-containing (meth)acrylicpolymer (C). If the amount is less than 5 parts by weight, the effectsof the plasticizer cannot be obtained. If the amount is more than 150parts by weight, the mechanical strength of the cured product isinsufficient. One plasticizer may be used alone, or two or moreplasticizers may be used in combination. Also, a low-molecular-weightplasticizer and a polymer plasticizer may be used in combination.Moreover, the plasticizer may be added at the time of polymerproduction.

The curable composition of the present invention may further incorporatea silane coupling agent, a reaction product of a silane coupling agent,or a compound other than silane coupling agents as an adhesion-impartingagent. Specific examples of the silane coupling agent include:isocyanato group-containing silanes such asγ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane,γ-isocyanatopropylmethyldiethoxysilane,γ-isocyanatopropylmethyldimethoxysilane,α-isocyanatomethyltrimethoxysilane, andα-isocyanatomethyldimethoxymethylsilane; amino group-containing silanessuch as γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane,γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane,N-β-aminoethyl-γ-aminopropyltrimethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane,N-β-aminoethyl-γ-aminopropyltriethoxysilane,N-β-aminoethyl-γ-aminopropylmethyldiethoxysilane,γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane,N-benzyl-γ-aminopropyltrimethoxysilane, andN-vinylbenzyl-γ-aminopropyltriethoxysilane; mercapto group-containingsilanes such as γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane,and γ-mercaptopropylmethyldiethoxysilane; epoxy group-containing silanessuch as γ-glycidoxypropyltrimethoxysilane,γ-glycidoxypropyltriethoxysilane,γ-glycidoxypropylmethyldimethoxysilane,β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, andβ-(3,4-epoxycyclohexyl)ethyltriethoxysilane; carboxysilanes such asβ-carboxyethyltriethoxysilane, β-carboxyethylphenylbis((3-methoxyethoxy)silane, andN-β-(carboxymethyl)aminoethyl-γ-aminopropyltrimethoxysilane; vinylunsaturated group-containing silanes such as vinyltrimethoxysilane,vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, andγ-acryloyloxypropylmethyltriethoxysilane; halogen-containing silanessuch as γ-chloropropyltrimethoxysilane; and isocyanurate silanes such astris (trimethoxysilyl)isocyanurate. Moreover, derivatives obtained bymodifying these, for example, amino-modified silyl polymers, silylatedamino polymers, unsaturated aminosilane complexes, phenylaminolong-chain alkylsilanes, aminosilylated silicones, and silylatedpolyesters, may be used as the silane coupling agent. The silanecoupling agent that can be used in the present invention is preferablyused in the range of 0.1 to 20 parts by weight, particularly preferablyin the range of 0.5 to 10 parts by weight, for each 100 parts by weightin total of the reactive silyl group-containing polyether polymer (A),and the reactive silyl group-containing polyether polymer (B) and/or thereactive silyl group-containing (meth)acrylic polymer (C).

The curable composition of the present invention may further incorporatevarious fillers. Examples of the fillers include reinforcing fillerssuch as fumed silica, precipitated silica, crystalline silica, fusedsilica, dolomite, silicic anhydride, hydrous silicic acid, and carbonblack; fillers such as heavy calcium carbonate, colloidal calciumcarbonate, magnesium carbonate, diatomite, calcined clay, clay, talc,titanium oxide, bentonite, organic bentonite, ferric oxide, finealuminum powder, flint powder, zinc oxide, activated zinc white, andresin powders including PVC powder and PMMA powder; and fibrous fillerssuch as asbestos, glass fiber, and filaments. In the case of using thefiller, the amount thereof is 1 to 300 parts by weight, preferably 10 to200 parts by weight, for each 100 parts by weight in total of thereactive silyl group-containing polyether polymer (A), and the reactivesilyl group-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer (C).

In order to obtain a cured product having higher strength by the use ofsuch a filler, the filler is preferably selected mainly from fumedsilica, precipitated silica, crystalline silica, fused silica, dolomite,silicic anhydride, hydrous silicic acid, carbon black, surface-treatedfine calcium carbonate, calcined clay, clay, activated zinc white andthe like. This filler provides favorable results when its amount used isin the range of 1 to 200 parts by weight for each 100 parts by weight intotal of the reactive silyl group-containing polyether polymer (A), andthe reactive silyl group-containing polyether polymer (B) and/or thereactive silyl group-containing (meth)acrylic polymer (C). In order toobtain a cured product having low strength and high elongation at break,a filler mainly selected from titanium oxide, calcium carbonate,magnesium carbonate, talc, ferric oxide, zinc oxide, shirasu balloonsand the like is used in the range of 5 to 200 parts by weight for each100 parts by weight in total of the reactive silyl group-containingpolyether polymer (A), and the reactive silyl group-containing polyetherpolymer (B) and/or the reactive silyl group-containing (meth)acrylicpolymer (C), which provides favorable results.

Generally, calcium carbonate with a greater specific surface area has alarger effect in improving the tensile strength at break, elongation atbreak, and adhesion of the cured product. Of course each of thesefillers may be used alone, or two or more of these may be used inadmixture. Colloidal calcium carbonate surface-treated with fatty acidmay be used in combination with calcium carbonate having a particle sizeof 1 μm or greater, such as heavy calcium carbonate that is notsurface-treated.

The curable composition of the present invention may further containhollow spheres such as balloons for the purpose of reducing the weight(or specific gravity) of the composition.

Balloons are spherical fillers having a hollow inside. Examples of thematerial of the balloons include, but not limited to, inorganicmaterials such as glass, shirasu, and silica; and organic materials suchas phenolic resin, urea resin, polystyrene, Saran and acrylnitrile. Aninorganic material and an organic material may be formed into acomposite or may be layered to form a multilayer. Inorganic, organic, ortheir composite balloons may be used. Also, a single type of balloonsmay be used, or a mixture of multiple types of balloons made ofdifferent materials may be used. Moreover, the surface of balloons to beused may be processed or coated, or may be treated with various surfacetreating agents. For example, organic balloons may be coated withcalcium carbonate, talc, titanium oxide, or the like, or inorganicballoons may be surface-treated with a silane coupling agent.

The particle size of balloons is preferably 3 to 200 μm, andparticularly preferably 10 to 110 μm. Balloons having a particle sizeless than 3 μm make a small contribution to the weight reduction andthus need to be added in large amounts. Balloons having a particle sizeof 200 μm or greater are likely to make the surface of the cured sealingmaterial irregular, and to reduce the elongation.

In the case of using balloons, it is possible to add the following: ananti-slip agent as described in JP-A 2000-154368, and an amine compoundfor giving a matte appearance as well as an irregular appearance to thesurface of the cured product, particularly a primary and/or secondaryamines with a melting point of 35° C. or higher, as described in JP-A2001-164237.

Specific examples of the balloons include ones described in JP-AH02-129262, JP-A H04-8788, JP-A H04-173867, JP-A H05-1225, JP-AH07-113073, JP-A H09-53063, JP-A H10-251618, JP-A 2000-154368, JP-A2001-164237, and WO 97/05201.

The amount of hollow spheres is preferably 0.01 to 30 parts by weightfor each 100 parts by weight in total of the reactive silylgroup-containing polyether polymer (A), and the reactive silylgroup-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer (C). The lower limit thereof ismore preferably 0.1 parts by weight, and the upper limit is morepreferably 20 parts by weight. Less than 0.01 parts by weight of hollowspheres are unlikely to be effective in improving the workability. Morethan 30 parts by weight of hollow spheres are likely to decrease theelongation and the tensile strength at break of the cured product.

The curable composition of the present invention may optionallyincorporate a physical-property modifier in order to adjust the tensileproperties of a cured product to be obtained. Examples of thephysical-property modifier include, but not limited to:alkylalkoxysilanes such as methyltrimethoxysilane,dimethyldimethoxysilane, trimethylmethoxysilane, andn-propyltrimethoxysilane; alkylisopropenoxysilanes such asdimethyldiisopropenoxysilane, methyltriisopropenoxysilane, andγ-glycidoxypropylmethyldiisopropenoxysilane; functional group-containingalkoxysilanes such as γ-glycidoxypropylmethyldimethoxysilane,γ-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane,vinyldimethylmethoxysilane, γ-aminopropyltrimethoxysilane,N-β-aminoethyl-β-aminopropylmethyldimethoxysilane,γ-mercaptopropyltrimethoxysilane, andγ-mercaptopropylmethyldimethoxysilane; silicone varnishes; andpolysiloxanes. Use of the physical-property modifier can increase thehardness of the cured composition in the present invention or,conversely, decrease the hardness to offer elongation at break. Each ofthe physical-property modifiers may be used alone, or two or more ofthese may be used in combination.

In particular, compounds that generate a compound containing amonovalent silanol group in the molecule by hydrolysis serve to decreasethe modulus of the cured product without deteriorating the stickiness ofthe surface of the cured product. Particularly preferred are compoundsgenerating trimethylsilanol. Examples of the compounds that generate acompound containing a monovalent silanol group in the molecule byhydrolysis include compounds disclosed in JP-A H05-117521. Otherexamples include compounds that are derivatives of alkyl alcohols suchas hexanol, octanol, and decanol, and generate a silicon compoundgenerating a trialkylsilanol such as trimethylsilanol by hydrolysis; andcompounds that are derivatives of polyalcohols having three or morehydroxy groups such as trimethylolpropane, glycerol, pentaerythritol,and sorbitol, and generate a silicon compound generating atrialkylsilanol such as trimethylsilanol by hydrolysis, as disclosed inJP-A H11-241029.

Other examples also include compounds that are derivatives ofoxyalkylene polymers and generate a silicon compound generating atrialkylsilanol such as trimethylsilanol by hydrolysis, as disclosed inJP-A H07-258534; and polymers that contain a hydrolyzable silyl groupthat can be crosslinked and a silyl group that can form amonosilanol-containing compound by hydrolysis, as disclosed in JP-AH06-279693.

The physical-property modifier is used in the range of 0.1 to 20 partsby weight, preferably 0.5 to 10 parts by weight, for each 100 parts byweight in total of the reactive silyl group-containing polyether polymer(A), and the reactive silyl group-containing polyether polymer (B)and/or the reactive silyl group-containing (meth)acrylic polymer (C).

The curable composition of the present invention may optionallyincorporate an anti-sagging agent to prevent sagging and improve theworkability. Examples of the anti-sagging agent include, but not limitedto, polyamide waxes, hydrogenated castor oil derivatives, and metalsoaps such as calcium stearate, aluminum stearate, and barium stearate.Each of these anti-sagging agents may be used alone, or two or more ofthese may be used in combination.

The anti-sagging agent is used in the range of 0.1 to 20 parts by weightfor each 100 parts by weight in total of the reactive silylgroup-containing polyether polymer (A), and the reactive silylgroup-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer (C).

The curable composition of the present invention may contain anantioxidant (age resistor). Use of an antioxidant enhances the weatherresistance of the cured product. Examples of the antioxidant includehindered phenol antioxidants, monophenol antioxidants, bisphenolantioxidants, and polyphenol antioxidants. Particularly preferred arehindered phenol antioxidants. Similarly, the following hindered aminelight stabilizers can be used: Tinuvin 622LD, Tinuvin 144; CHIMASSORB944LD, and CHIMASSORB 119FL (all are products of Ciba Japan); ADK STABLA-57, ADK STAB LA-62, ADK STAB LA-67, ADK STAB LA-63, and ADK STABLA-68 (all are products of ADEKA Corporation); and SANOL LS-770, SANOLLS-765, SANOL LS-292, SANOL LS-2626, SANOL LS-1114, and SANOL LS-744(all are products of Sankyo Lifetech Co., Ltd.). Specific examples ofthe antioxidant also include ones disclosed in JP-A H04-283259 and JP-AH09-194731.

The amount of antioxidant is preferably 0.1 to 10 parts by weight, andmore preferably 0.2 to 5 parts by weight, for each 100 parts by weightin total of the reactive silyl group-containing polyether polymer (A),and the reactive silyl group-containing polyether polymer (B) and/or thereactive silyl group-containing (meth)acrylic polymer (C).

The curable composition of the present invention may contain a lightstabilizer. Use of a light stabilizer enables to prevent photooxidativedegradation of the cured product. Examples of the light stabilizerinclude benzotriazole compounds, hindered amine compounds, and benzoatecompounds. Particularly preferred are hindered amine compounds.

The amount of light stabilizer is preferably 0.1 to 10 parts by weight,and more preferably 0.2 to 5 parts by weight, for each 100 parts byweight in total of the reactive silyl group-containing polyether polymer(A), and the reactive silyl group-containing polyether polymer (B)and/or the reactive silyl group-containing (meth)acrylic polymer (C).Specific examples of the light stabilizer include ones described in JP-AH09-194731.

In the case that the curable composition of the present inventioncontains a photo-curable substance, particularly an unsaturated acryliccompound, then a tertiary amine-containing hindered amine lightstabilizer is preferably used as the hindered amine light stabilizer interms of improving the storage stability of the composition, as taughtin JP-A H05-70531. Examples of the tertiary amine-containing hinderedamine light stabilizer include Tinuvin 622LD, Tinuvin 144, andCHIMASSORB 119FL (all are products of Ciba Japan); ADK STAB LA-57,LA-62, LA-67, and LA-63 (all are products of ADEKA Corporation); andSANOL LS-765, LS-292, LS-2626, LS-1114, and LS-744 (all are products ofSankyo Lifetech Co., Ltd.).

The curable composition of the present invention may contain anultraviolet absorber. Use of an ultraviolet absorber enables to increasethe surface weather resistance of the cured product. Examples of theultraviolet absorber include benzophenone compounds, benzotriazolecompounds, salicylate compounds, substituted tolyl compounds, and metalchelate compounds. Particularly preferred are benzotriazole compounds.

The amount of ultraviolet absorber is preferably 0.1 to 10 parts byweight, and more preferably 0.2 to 5 parts by weight, for each 100 partsby weight in total of the reactive silyl group-containing polyetherpolymer (A), and the reactive silyl group-containing polyether polymer(B) and/or the reactive silyl group-containing (meth)acrylic polymer(C). It is preferable to use a phenol or hindered phenol antioxidant, ahindered amine light stabilizer, and a benzotriazole ultravioletabsorber in combination.

The curable composition of the present invention may optionallyincorporate various additives for the adjustment of physical propertiesof the curable composition or cured product. Examples of the additivesinclude flame retardants, curability modifiers, radical inhibitors,metal deactivators, antiozonants, phosphorus-containing peroxidedecomposers, lubricants, pigments, blowing agents, solvents, andantifungal agents. Each of these various additives may be used alone, ortwo or more of these may be used in combination. Specific examples ofadditives other than the ones mentioned herein are described in, forexample, JP-B H04-69659, JP-B H07-108928, JP-A S63-254149, JP-AS64-22904, and JP-A 2001-72854.

The curable composition of the present invention can be prepared as aone-pack curable composition which is prepared by compounding all theformulation components and storing the resulting composition in ahermetically closed vessel in advance, and after application, is curableby moisture in the air. Also, the curable composition can be prepared asa two-pack curable composition which separately includes components tobe mixed with each other prior to application, namely a polymercomposition and a mixture as curing agent that is separately prepared bymixing components including a curing catalyst, filler, plasticizer, andwater.

In the case of preparing a one-pack curable composition, since all theformulation components are mixed in advance, it is preferable thatformulation components containing water be dehydrated and dried prior toapplication, or be dehydrated, for example, under reduced pressureduring the mixing and kneading. In the case of preparing a two-packcurable composition, since a curing catalyst is not required to be mixedin the base mixture including the reactive silyl group-containingorganic polymers, the base mixture is less likely to be gelled even if asmall amount of water is left; still, if long-term storage stability isrequired, it is preferable that the formulation components be dehydratedand dried. Preferred examples of the dehydrating and drying methodinclude heat drying in the case that the formulation components aresolids such as powder; and vacuum dehydration or dehydration using asubstance such as synthetic zeolite, active alumina, and silica gel inthe case that the formulation components are liquids. Also, thecomposition may be mixed with a small amount of an isocyanato compoundso that the isocyanato group and water are reacted for dehydration. Thestorage stability can be further improved by, in addition to performingthe dehydrating and drying method mentioned above, adding a loweralcohol such as methanol and ethanol; or an alkoxysilane compound suchas n-propyltrimethoxysilane, vinyltrimethoxysilane,vinylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane, andγ-glycidoxypropyltrimethoxysilane.

The amount of dehydrating agent, particularly a silicon compoundreactive with water, such as vinyltrimethoxysilane, is 0.1 to 20 partsby weight, preferably 0.5 to 10 parts by weight, for each 100 parts byweight in total of the reactive silyl group-containing polyether polymer(A), and the reactive silyl group-containing polyether polymer (B)and/or the reactive silyl group-containing (meth)acrylic polymer (C).

The curable composition of the present invention can be used in variousapplications such as floor adhesives; coating agents; pressure-sensitiveadhesives; impression materials; vibration-proof materials; dampingmaterials; soundproof materials; expanded/foamed materials; coatingcompositions; spray coatings; electric and electronic part materials(e.g. solar cell backside sealants); electrical insulating materials(e.g. insulating coating materials for electric wires and cables);elastic adhesives; contact adhesives; spray sealants; crack repairmaterials; tiling adhesives; powder coating compositions; castingmaterials; rubber materials for medical use; pressure-sensitiveadhesives for medical use; sealing materials for medical devices; foodpackaging materials; joint sealing materials for siding boards and otherexterior materials; primers; electromagnetic-wave-shielding conductivematerials; thermally conductive materials; hot melt materials; pottingagents for electrics and electronics; films; gaskets; various moldingmaterials; rustproof and waterproof encapsulants for wired glass andlaminated-glass edges (cut end faces); and liquid sealants for use inautomotive parts, electrical machinery parts, various machinery parts,and the like. Furthermore, the curable composition may also be used asvarious sealing compositions and adhesive compositions because it,either alone or with the aid of a primer, can adhere to a wide range ofsubstrates such as glass, ceramics, wood, metals, and resin moldings. Inaddition, the curable composition of the present invention may also beused as adhesives for interior panels, adhesives for exterior panels,stone pitching adhesives, ceiling finishing adhesives, floor finishingadhesives, wall finishing adhesives, vehicle panel adhesives, andadhesives for electric/electronic/precision device assembling.

EXAMPLES

Hereinafter, the present invention will be described in more detail withreference to specific examples. They are, however, by no meanslimitative of the scope of the present invention.

Chloromethyldimethoxysilane used in the following synthesis examples wassynthesized by synthesizing chloromethyldichlorosilane by the methoddescribed in Example 41 of WO 2010/004948 and methoxylating the compoundby the method described in Example 55 thereof.

Synthesis Example 1

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a molecular weight of about 2,000 as an initiator and a zinchexacyanocobaltate glyme complex catalyst to provide polyoxypropylenediol having a number average molecular weight of 21,100(polystyrene-equivalent molecular weight determined with a solventdelivery system: HLC-8120 GPC produced by TOSOH; a column: TSK-GEL Htype produced by TOSOH; and a solvent: THF). To this polyoxypropylenediol was then added a methanol solution of NaOMe in an amount of 1.2equivalents relative to the hydroxy groups of the polyoxypropylene diol,and the methanol was distilled off. 3-Chloro-1-propene was then added tothe residue, and thereby the terminal hydroxy group was converted to anallyl group. To 100 parts by weight of the obtained allyl-terminatedpolyoxypropylene polymer were then added 72 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight) and 1.29 parts by weight of trimethylorthoformate and then gradually added dropwise 1.51 parts of(chloromethyl)dimethoxysilane with stirring. The mixed solution wasreacted at 90° C. for 2 hours to provide achloromethyldimethoxysilyl-terminated linear polyoxypropylene polymer(A-1) containing 1.5 reactive silyl groups on average per molecule andhaving a number average molecular weight of 21,100.

Synthesis Example 2

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a molecular weight of about 2,000 as an initiator and a zinchexacyanocobaltate glyme complex catalyst to provide polyoxypropylenediol having a number average molecular weight of 28,500 (calculated inthe same way as in Synthesis Example 1). To this polyoxypropylene diolwas then added a methanol solution of NaOMe in an amount of 1.2equivalents relative to the hydroxy groups of the polyoxypropylene diol,and the methanol was distilled off. 3-Chloro-1-propene was then added tothe residue, and thereby the terminal hydroxy group was converted to anallyl group. To 100 parts by weight of the obtained allyl-terminatedpolyoxypropylene polymer were then added 72 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight) and 1.05 parts by weight of trimethylorthoformate and then gradually added dropwise 1.22 parts of(chloromethyl)dimethoxysilane with stirring. The mixed solution wasreacted at 90° C. for 2 hours to provide a(chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer(A-2) containing 1.5 reactive silyl groups on average per molecule andhaving a number average molecular weight of 28,500.

Synthesis Example 3

Propylene oxide was polymerized in the presence of polyoxypropylenetriol having a number average molecular weight of about 3,000 as aninitiator and a zinc hexacyanocobaltate glyme complex catalyst toprovide polyoxypropylene triol having a number average molecular weightof 26,200 (calculated in the same way as in Synthesis Example 1). Tothis polyoxypropylene triol was then added a methanol solution of NaOMein an amount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene triol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 72 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight) and 0.79 parts byweight of trimethyl orthoformate and then gradually added dropwise 1.83parts by weight of (chloromethyl)dimethoxysilane with stirring. Themixed solution was reacted at 90° C. for 2 hours to provide achloromethyl dimethoxysilyl-terminated branched polyoxypropylene polymer(A-3) containing 2.3 reactive silyl groups on average per molecule andhaving a number average molecular weight of 26,200.

Synthesis Example 4

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 14,600(calculated in the same way as in Synthesis Example 1). To thispolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 72 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight) and 2.01 parts byweight of trimethyl orthoformate and then was gradually added dropwise2.35 parts by weight of (chloromethyl)dimethoxysilane with stirring. Themixed solution was reacted at 90° C. for 2 hours to provide a(chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer(A-4) containing 1.5 reactive silyl groups on average per molecule andhaving a number average molecular weight of 14,600.

Synthesis Example 5

Acetyl chloride (4 molar equivalents) was allowed to act on(methoxymethyl)trimethoxysilane produced with reference to the methoddescribed in Example 2 of JP-T 2007-513203, in the presence of 0.02molar equivalent of zinc chloride as a catalyst.(Methoxymethyl)trichlorosilane was synthesized by reaction for 36 hoursunder reflux conditions by heating.

(Methoxymethyl)trichlorosilane purified by distillation was mixed with 1molar equivalent of methyldichlorosilane (LS-50, a product of Shin-EtsuChemical Co., Ltd.). To the mixture was then added 0.05 molar equivalentof methyl tributylammonium chloride. The mixture was then allowed toreact for 3 hours under reflux conditions by heating. As a result,methoxymethyldichlorosilane was obtained at a conversion rate of about50%.

To a reaction vessel was added trimethyl orthoacetate in an amount of2.5 molar equivalents relative to (methoxymethyl)dichlorosilane purifiedby distillation, and was further gradually added(methoxymethyl)dichlorosilane with sufficient stirring. The additionrate was adjusted so as to keep the reaction solution at a temperatureof not higher than 50° C. After the completion of addition, it wasconfirmed from ¹H-NMR spectra (measured in a CDCl₃ solvent withJNM-LA400 produced by JEOL Ltd.; analysis was conducted with the peak ofCHCL₃ as 7.26 ppm) that (methoxymethyl)dichlorosilane was almostquantitatively converted to (methoxymethyl)dimethoxysilane. Theresultant was purified by distillation under reduced pressure to obtain(methoxymethyl)dimethoxysilane.

¹HNMR spectral assignment: δ4.52 (t, 1H), 3.60 (s, 6H), 3.35 (s, 3H),3.19 (d, 2H).

Synthesis Example 6

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 14,600(calculated in the same way as in Synthesis Example 1). To thishydroxy-terminated polyoxypropylene diol was then added a methanolsolution of NaOMe in an amount of 1.2 equivalents relative to thehydroxy groups of the polyoxypropylene diol, and the methanol wasdistilled off. 3-Chloro-1-propene was then added to the residue, andthereby the terminal hydroxy group was converted to an allyl group. To100 parts by weight of the obtained allyl-terminated polyoxypropylenepolymer were then added 72 ppm of a platinum-divinyldisiloxane complex(isopropanol solution having a platinum content of 3% by weight) and2.01 parts by weight of trimethyl orthoformate and then was graduallyadded dropwise 2.28 parts by weight of (methoxymethyl)dimethoxysilanesynthesized in Synthesis Example 5 with stirring. The mixed solution wasreacted at 90° C. for 2 hours to provide a(methoxymethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer(A-5) containing 1.5 reactive silyl groups on average per molecule andhaving a number average molecular weight of 14,600.

Synthesis Example 7

A reactor was charged with 71.1 g (0.88 mol) of potassium cyanate andpurged with nitrogen. To the reactor were added 500 ml ofN,N-dimethylformamide and then 125.0 g (0.75 mol) ofchloromethyl-dimethoxymethylsilane and 50.2 g (1.56 mol) of methanolwhile the mixture was sufficiently stirred. The resulting mixture washeated to 90° C., then heated to 120° C. over 4 hours, and furtherstirred for 3 hours. The deposited potassium chloride was filtered off,and the N,N-dimethylformamide was distilled off using an evaporator. Theresidue was then purified by distillation to providemethyl(N-dimethoxymethylsilylmethyl)carbamate (MeCO₂NH—CH₂—Si(OMe)₂Me)(yield: 116.2 g).

A reactor connected with a fractionating column and a condenser wascharged with 100 g (0.52 mol) of the obtainedmethyl(N-dimethoxymethylsilylmethyl)carbamate and 13 mg (0.002 mmol) ofdibutyltin dilaurate, and the pressure in the system was reduced to 45mmHg. The mixture was heated to 170° C. While the degradation reactionproduct methanol was separated and collected,(isocyanatomethyl)dimethoxymethylsilane (OCN—CH₂—SiCH₃(OCH₃)₂) wassynthesized over 5 hours. The resultant was purified by distillationunder reduced pressure to obtain (isocyanatomethyl)dimethoxymethylsilane(yield: 50 g).

Synthesis Example 8

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 14,600(calculated in the same way as in Synthesis Example 1). To 100 parts byweight of the obtained polyoxypropylene diol was added 30 ppm ofdibutyltin dilaurate and was then gradually added dropwise(isocyanatomethyl)dimethoxymethylsilane (3.1 parts by weight)synthesized in Synthesis Example 7 with stirring. The mixed solution wasreacted at 90° C. for 3 hours and then deaerated for 2 hours to providea dimethoxymethylsilyl-terminated linear polyoxypropylene polymer (A-6)containing 1.8 reactive silyl groups on average per molecule and havinga number average molecular weight of 14,600.

Synthesis Example 9

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 28,500(calculated in the same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-2-methyl-1-propene was then added to the residue, and therebythe terminal hydroxy group was converted to a methallyl group. Thecontainer was then purged with 6% O₂/N₂. To 100 parts by weight of theobtained methallyl-terminated polyoxypropylene polymer were then added100 ppm of sulfur (0.25 wt % solution in hexane), 100 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight), and 1.37 parts by weight of trimethylorthoformate and then gradually added dropwise 1.60 parts by weight of(chloromethyl)dimethoxysilane with stirring. The mixed solution wasreacted at 100° C. for 5 hours to provide a(chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer(A-7) containing 1.9 reactive silyl groups on average per molecule andhaving a number average molecular weight of 28,500.

Synthesis Example 10

Propylene oxide was polymerized in the presence of butanol as aninitiator and a zinc hexacyanocobaltate glyme complex catalyst toprovide polyoxypropylene oxide having a number average molecular weightof 7,000 (calculated in the same way as in Synthesis Example 1). To thishydroxy-terminated polyoxypropylene oxide was then added a methanolsolution of NaOMe in an amount of 1.2 equivalents relative to thehydroxy groups of the hydroxy-terminated polyoxypropylene oxide, and themethanol was distilled off. 3-Chloro-1-propene was then added to theresidue, and thereby the terminal hydroxy group was converted to anallyl group. To 100 parts by weight of the obtained allyl-terminatedpolyoxypropylene polymer were then added 72 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight), and 1.95 parts by weight of trimethylorthoformate and then gradually added dropwise 2.28 parts by weight of(chloromethyl)dimethoxysilane with stirring. The mixed solution wasreacted at 90° C. for 2 hours to provide achloromethyldimethoxysilyl-terminated linear polyoxypropylene polymer(A-8) containing 0.7 reactive silyl groups on average per molecule andhaving a number average molecular weight of 7,000.

Synthesis Example 11

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 7,200(calculated in the same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 72 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight), and 3.83 parts byweight of trimethyl orthoformate and then gradually added dropwise 4.49parts by weight of (chloromethyl)dimethoxysilane with stirring. Themixed solution was reacted at 90° C. for 2 hours to provide a(chloromethyl)dimethoxysilyl-terminated linear polyoxypropylene polymer(A-9) containing 1.5 reactive silyl groups on average per molecule andhaving a number average molecular weight of 7,400.

Synthesis Example 12

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a molecular weight of about 2,000 as an initiator and a zinchexacyanocobaltate glyme complex catalyst to provide polyoxypropylenediol having a number average molecular weight of 21,100 (calculated inthe same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer wasadded 36 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight), and was thengradually added dropwise 1.15 parts by weight of dimethoxymethylsilanewith stirring. The mixed solution was reacted at 90° C. for 2 hours toprovide a dimethoxymethylsilyl-terminated linear polyoxypropylenepolymer (B-1) containing 1.5 reactive silyl groups on average permolecule and having a number average molecular weight of 21,100.

Synthesis Example 13

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a molecular weight of about 2,000 as an initiator and a zinchexacyanocobaltate glyme complex catalyst to provide polyoxypropylenediol having a number average molecular weight of 28,500 (calculated inthe same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 36 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight), and then graduallyadded dropwise 0.96 parts by weight of dimethoxymethylsilane withstirring. The mixed solution was reacted at 90° C. for 2 hours toprovide a dimethoxymethylsilyl-terminated linear polyoxypropylenepolymer (B-2) containing 1.5 reactive silyl groups on average permolecule and having a number average molecular weight of 28,500.

Synthesis Example 14

Propylene oxide was polymerized in the presence of polyoxypropylenetriol having a number average molecular weight of about 3,000 as aninitiator and a zinc hexacyanocobaltate glyme complex catalyst toprovide polyoxypropylene triol having a number average molecular weightof 26,200 (calculated in the same way as in Synthesis Example 1). To theobtained polyoxypropylene triol was then added a methanol solution ofNaOMe in an amount of 1.2 equivalents relative to the hydroxy groups ofthe polyoxypropylene triol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 36 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight), and then graduallyadded dropwise 1.29 parts by weight of dimethoxymethylsilane withstirring. The mixed solution was reacted at 90° C. for 2 hours toprovide a dimethoxymethylsilyl-terminated branched polyoxypropylenepolymer (B-3) containing 2.3 reactive silyl groups on average permolecule and having a number average molecular weight of 26,200.

Synthesis Example 15

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 28,500(calculated in the same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-2-methyl-1-propene was then added to the residue, and therebythe terminal hydroxy group was converted to a methallyl group. Thecontainer was then purged with 6% O₂/N₂. To 100 parts by weight of theobtained methallyl-terminated polyoxypropylene polymer were then added100 ppm of sulfur (0.25 wt % solution in hexane), 100 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight), and then gradually added dropwise2.30 parts by weight of dimethoxymethylsilane with stirring. The mixedsolution was reacted at 100° C. for 5 hours to provide adimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-4)containing 1.9 reactive silyl groups on average per molecule and havinga number average molecular weight of 28,500.

Synthesis Example 16

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a number average molecular weight of about 2,000 as an initiatorand a zinc hexacyanocobaltate glyme complex catalyst to providepolyoxypropylene diol having a number average molecular weight of 28,500(calculated in the same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer wasadded 36 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight) and was thengradually added dropwise TES (triethoxysilane) (1.48 parts by weight)with stirring. The mixed solution was reacted at 90° C. for 2 hours.Then 20 parts by weight of methanol and 12 ppm of HCl were further addedto the reaction solution, and thereby the terminal ethoxy group wasconverted to a methoxy group to provide a trimethoxysilyl-terminatedlinear polyoxypropylene polymer (B-5) containing 1.6 reactive silylgroups on average per molecule and having a number average molecularweight of 28,500.

Synthesis Example 17

Propylene oxide was polymerized in the presence of butanol as aninitiator and a zinc hexacyanocobaltate glyme complex catalyst toprovide polyoxypropylene oxide having a number average molecular weightof 7,000 (calculated in the same way as in Synthesis Example 1). To thishydroxy-terminated polyoxypropylene oxide was then added a methanolsolution of NaOMe in an amount of 1.2 equivalents relative to thehydroxy groups of the hydroxy-terminated polyoxypropylene oxide, and themethanol was distilled off. 3-Chloro-1-propene was then added to theresidue, and thereby the terminal hydroxy group was converted to anallyl group. To 100 parts by weight of the obtained allyl-terminatedpolyoxypropylene polymer were then added 36 ppm of aplatinum-divinyldisiloxane complex (isopropanol solution having aplatinum content of 3% by weight), and then gradually added dropwise1.72 parts by weight of dimethoxymethylsilane with stirring. The mixedsolution was reacted at 90° C. for 2 hours to provide adimethoxymethylsilyl-terminated linear polyoxypropylene polymer (B-6)containing 0.7 reactive silyl groups on average per molecule and havinga number average molecular weight of 7,000.

Synthesis Example 18

Propylene oxide was polymerized in the presence of polyoxypropylene diolhaving a molecular weight of about 2,000 as an initiator and a zinchexacyanocobaltate glyme complex catalyst to provide polyoxypropylenediol having a number average molecular weight of 14,500 (calculated inthe same way as in Synthesis Example 1). To the obtainedpolyoxypropylene diol was then added a methanol solution of NaOMe in anamount of 1.2 equivalents relative to the hydroxy groups of thepolyoxypropylene diol, and the methanol was distilled off.3-Chloro-1-propene was then added to the residue, and thereby theterminal hydroxy group was converted to an allyl group. To 100 parts byweight of the obtained allyl-terminated polyoxypropylene polymer werethen added 36 ppm of a platinum-divinyldisiloxane complex (isopropanolsolution having a platinum content of 3% by weight), and then graduallyadded dropwise 1.77 parts by weight of dimethoxymethylsilane withstirring. The mixed solution was reacted at 90° C. for 2 hours toprovide a dimethoxymethylsilyl-terminated linear polyoxypropylenepolymer (B-7) containing 1.5 reactive silyl groups on average permolecule and having a number average molecular weight of 14,500.

Synthesis Example 19

To polyoxypropylene diol having a number average molecular weight of4,200 (calculated in the same way as in Synthesis Example 1) was added amethanol solution of NaOMe in an amount of 1.2 equivalents relative tothe hydroxy groups of the polyoxypropylene diol, and the methanol wasdistilled off. 3-Chloro-1-propene was then added to the residue, andthereby the terminal hydroxy group was converted to an allyl group. To100 parts by weight of the obtained allyl-terminated polyoxypropylenepolymer were then added 36 ppm of a platinum-divinyldisiloxane complex(isopropanol solution having a platinum content of 3% by weight), andthen gradually added dropwise 3.80 parts by weight ofdimethoxymethylsilane with stirring. The mixed solution was reacted at90° C. for 2 hours to provide a dimethoxymethylsilyl-terminated linearpolyoxypropylene polymer (B-8) containing 1.0 reactive silyl groups onaverage per molecule and having a number average molecular weight of4,200.

Synthesis Example 20

A four-neck flask equipped with a stirrer was charged with 44.7 parts byweight of isobutanol, and the internal temperature of the flask wasraised to 105° C. in a nitrogen atmosphere. To the flask was then addeddropwise over 5 hours a mixed solution containing 72.9 parts by weightof methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6parts by weight of stearyl methacrylate, 6.0 parts by weight of3-methacryloxypropylmethyldimethoxysilane, 7.9 parts by weight of3-mercaptopropylmethyldimethoxysilane, and 2.7 parts by weight of2,2′-azobis(2-methylbutyronitrile) dissolved in 24.3 parts by weight ofisobutanol. The reaction mixture was then subjected to polymerization at105° C. for 2 hours to provide an isobutanol solution (solid content:60%) of a reactive silyl group-containing (meth)acrylic polymer (C-1)containing 1.6 silyl groups on average per molecule and having a numberaverage molecular weight of 2,000 (calculated in the same way as inSynthesis Example 1).

Synthesis Example 21

A four-neck flask equipped with a stirrer was charged with 45.5 parts byweight of isobutanol, and the internal temperature of the flask wasraised to 105° C. in a nitrogen atmosphere. To the flask was then addeddropwise over 5 hours a mixed solution containing 72.5 parts by weightof methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6parts by weight of stearyl methacrylate, 6.4 parts by weight of3-methacryloxypropyltrimethoxysilane, 8.6 parts by weight of3-mercaptopropyltrimethoxysilane, and 2.7 parts by weight of2,2′-azobis(2-methylbutyronitrile) dissolved in 24.3 parts by weight ofisobutanol. The reaction mixture was then subjected to polymerization at105° C. for 2 hours to provide an isobutanol solution (solid content:60%) of a reactive silyl group-containing (meth)acrylic polymer (C-2)containing 1.6 silyl groups on average per molecule and having a numberaverage molecular weight of 2,000 (calculated in the same way as inSynthesis Example 1).

Synthesis Example 22

A four-neck flask equipped with a stirrer was charged with 45.4 parts byweight of isobutanol, and the internal temperature of the flask wasraised to 105° C. in a nitrogen atmosphere. To the flask was then addeddropwise over 5 hours a mixed solution containing 59.5 parts by weightof methyl methacrylate, 6.5 parts by weight of butyl acrylate, 14.6parts by weight of stearyl methacrylate, 19.4 parts by weight ofmethacryloxymethyltrimethoxysilane, 8.9 parts by weight ofn-dodecylmercaptan, and 2.7 parts by weight of 2,2′-azobis(2-methylbutyronitrile) dissolved in 24.3 parts by weight of isobutanol.The reaction mixture was then subjected to polymerization at 105° C. for2 hours to provide an isobutanol solution (solid content: 60%) of areactive silyl group-containing (meth)acrylic polymer (C-3) containing2.0 silyl groups on average per molecule and having a number averagemolecular weight of 2,000 (calculated in the same way as in SynthesisExample 1).

Synthesis Example 23

To a deoxygenated reactor were added 0.72 parts by weight of cuprousbromide, 13.4 parts by weight of butyl acrylate, 5.0 parts by weight ofethyl acrylate, and 1.6 parts by weight of stearyl acrylate, and themixture was heated with stirring. Then 8.8 parts by weight ofacetonitrile as a polymerization solvent and 1.50 parts by weight ofdiethyl 2,5-dibromoadipate as an initiator were added to the mixture andmixed therewith. When the temperature of the mixed solution was adjustedto about 80° C., polymerization reaction was started by the addition ofpentamethyldiethylenetriamine (hereinafter abbreviated to triamine). Thepolymerization reaction was then promoted by the addition of 53.6 partsby weight of butyl acrylate, 20 parts by weight of ethyl acrylate, and6.4 parts by weight of stearyl acrylate in order. During thepolymerization, triamine was appropriately added to adjust thepolymerization rate. The total amount of triamine used in thispolymerization was 0.15 parts by weight. When the monomer conversationrate (polymerization reaction rate) reached about 95% or more, thevolatile matter was removed by evaporation under reduced pressure toprovide a polymer concentrate.

To the concentrate were then added 21 parts by weight of 1,7-octadieneand 35 parts by weight of acetonitrile and was further added 0.34 partsby weight of triamine. While the internal temperature was adjusted toabout 80° C. to about 90° C., the mixture was stirred under heating forsome hours to react the polymer end with the octadiene. The acetonitrileand unreacted octadiene were removed by evaporation under reducedpressure to provide a concentrate containing an alkenyl-terminatedpolymer.

The concentrate was diluted with toluene. A filter aid, an adsorbent(Kyowaad 700SEN; product of Kyowa Chemical Industry Co., Ltd.), andhydrotalcite (Kyowaad 500SH; product of Kyowa Chemical Industry Co.,Ltd.) were added thereto, and the mixture was heated to about 80 to 100°C. and stirred. Then, solid components were filtered off. The filtratewas concentrated under reduced pressure to provide a crude polymer.

The crude polymer, a thermal stabilizer (SUMILIZER GS; product ofSumitomo Chemical Co., Ltd.), and adsorbents (Kyowaad 700SEN and Kyowaad500SH) were mixed. The mixture was evaporated under reduced pressurewhile being stirred under heating. The temperature was raised byheating, and the mixture was stirred under heating at a temperature ofas high as about 170° C. to about 200° C. for several hours while beingevaporated under reduced pressure. The reaction mixture was diluted withbutyl acetate, and the adsorbents were filtered off. The filtrate wasthen concentrated to obtain a polymer containing alkenyl groups at bothterminals.

To 100 parts by weight of the polymer thus obtained were then added 300ppm of a platinum-divinyldisiloxane complex (isopropanol solution havinga platinum content of 3% by weight) and 0.9 parts by weight of trimethylorthoformate and then gradually added dropwise 1.7 parts by weight ofdimethoxymethylsilane with stirring. The mixed solution was reacted at100° C. for 1 hour, and unreacted dimethoxymethylsilane was thendistilled off under reduced pressure to provide adimethoxymethylsilyl-terminated linear acrylic ester polymer (C-4)containing 1.9 reactive silyl groups on average per molecule and havinga number average molecular weight of 24,000.

Synthesis Example 24

To 40 parts by weight of toluene heated to 105° C. was added dropwiseover 5 hours a solution prepared by dissolving in 15 parts by weight oftoluene 67 parts by weight of methyl methacrylate, 5 parts by weight ofbutyl acrylate, 15 parts by weight of stearyl methacrylate, 5 parts byweight of 3-methacryloxypropylmethyldimethoxysilane, 8 parts by weightof γ-mercaptopropylmethyldimethoxysilane, and 3 parts by weight of2,2′-azobisisobutyronitrile as a polymerization initiator, and themixture was then stirred for 2 hours. A solution containing 0.3 parts byweight of 2,2′-azobisisobutyronitrile dissolved in 10 parts by weight oftoluene was further added thereto, and the mixture was stirred for 2hours to provide a toluene solution (solid content: 60%) of a reactivesilyl group-containing (meth)acrylic polymer (C-5) having 2.0 silylgroups on average per molecule and having a number average molecularweight of 3,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 25

To 40 parts by weight of toluene heated to 105° C. was added dropwiseover 5 hours a solution prepared by dissolving in 15 parts by weight oftoluene 66 parts by weight of methyl methacrylate, 5 parts by weight ofbutyl acrylate, 15 parts by weight of stearyl methacrylate, 5 parts byweight of 3-methacryloxypropyltrimethoxysilane, 9 parts by weight ofγ-mercaptopropyltrimethoxysilane, and 3 parts by weight of2,2′-azobisisobutyronitrile as a polymerization initiator, and themixture was then stirred for 2 hours. A solution containing 0.3 parts byweight of 2,2′-azobisisobutyronitrile dissolved in 10 parts by weight oftoluene was further added thereto, and the mixture was stirred for 2hours to provide a toluene solution (solid content: 60%) of a reactivesilyl group-containing (meth)acrylic polymer (C-6) having 2.0 silylgroups on average per molecule and having a number average molecularweight of 3,000 (calculated in the same way as in Synthesis Example 1).

Synthesis Example 26

To 40 parts by weight of toluene heated to 105° C. was added dropwiseover 5 hours a solution prepared by dissolving in 15 parts by weight oftoluene 66 parts by weight of methyl methacrylate, 10 parts by weight ofbutyl acrylate, 15 parts by weight of stearyl methacrylate, 9 parts byweight of n-dodecyl mercaptan, and 3 parts by weight of2,2′-azobisisobutyronitrile as a polymerization initiator, and themixture was then stirred for 2 hours. A solution containing 0.3 parts byweight of 2,2′-azobisisobutyronitrile dissolved in 10 parts by weight oftoluene was further added thereto, and the mixture was stirred for 2hours to provide a toluene solution (solid content: 60%) of a(meth)acrylic polymer (C′-7) having a number average molecular weight of3,000 (calculated in the same way as in Synthesis Example 1).

Example 1

With 100 parts by weight in total of the polymer (A-1) (70 parts byweight) and the polymer (B-1) (30 parts by weight) were mixed 50 partsby weight of fatty acid-treated calcium carbonate (product name:Hakuenka CCR, product of Shiraishi Kogyo Kaisha, Ltd.) and 50 parts byweight of heavy calcium carbonate (product name: Whiton SB Red, aproduct of Shiraishi Calcium Kaisha, Ltd.). The mixture was sufficientlykneaded and then dispersed by passing through triple paint rolls threetimes. Thereafter, the mixture was dehydrated under reduced pressure at120° C. for 2 hours and cooled to 50° C. or lower. To the mixture werethen added 4 parts by weight of vinyltrimethoxysilane (product name:A-171, a product of Momentive Performance Materials Inc.) as adehydrating agent, 3 parts by weight of γ-aminopropyltrimethoxysilane(product name: A-1110, a product of Momentive Performance MaterialsInc.) as an adhesion-imparting agent, and 0.3 parts by weight of DBU(1,8-diazabicyclo[5,4,0]undecene-7, product of Wako Pure ChemicalIndustries, Ltd.) as a condensation catalyst, and the mixture waskneaded under dehydrated conditions with substantially no water.Thereafter, the mixture was charged into a moisture-proof container(cartridge) and then hermetically packed therein to provide a one-packcurable composition.

(Evaluation)

The skin formation time and tensile properties of the preparedcomposition were determined by the following methods.

(Skin Formation Time)

In an atmosphere of 23° C. and 50% RH, each curable composition wassqueezed out of the cartridge and charged into a mold having a thicknessof about 5 mm with a spatula, and the time point at which the surface ofthe charged composition was flattened was defined as the start time ofcuring. The curing time was measured by touching the surface of thecomposition by a spatula from time to time, and determining the timeperiod required for the mixture to no longer stick to the spatula(regarded as skin formation time). Table 1 shows the results.

(Tensile Properties)

In an atmosphere of 23° C. and 50% RH, each curable composition wassqueezed out of the cartridge, and the mixture was charged into apolyethylene mold having a thickness of 3 mm so that no air bubble wastrapped. The charged composition was cured at 23° C. and 50% RH for 3days and then at 50° C. for 4 days to give a cured product. No. 3dumbbell-shaped specimens were punched out from the obtained curedproduct according to JIS K6251 and subjected to a tensile test (tensilerate: 200 mm/min., 23° C., 50% RH) to determine the tensile strength atbreak (TB) and the elongation at break (EB). Table 1 shows the results.

Examples 2 to 12 and 16 and Comparative Examples 1 to 12

Each curable composition was prepared in the same way as in Example 1except that the polymers (A), (B), and (C), plasticizer, filler,thixotropy-imparting agent, ultraviolet absorber, light stabilizer,dehydrating agent, adhesion-imparting agent, and catalyst were mixed atthe ratios of Examples 2 to 12 and 16 and Comparative Examples 1 to 12shown in Tables 1 to 3. The prepared compositions were evaluated. Tables1 and 3 show their respective results.

Example 13

A polymer mixture having a polymer weight ratio of (A-1)/(C-1)=60/40 wasprepared by mixing 60 parts by weight of the reactive silylgroup-containing polyoxypropylene polymer (A-1) obtained in SynthesisExample 1 with 66.7 parts by weight of the isobutanol solution of thereactive silyl group-containing (meth)acrylic polymer (C-1) obtained inSynthesis Example 20, and distilling off the isobutanol under reducedpressure. To 100 parts by weight of this polymer mixture were added 50parts by weight of fatty acid-treated calcium carbonate (product name:Hakuenka CCR, product of Shiraishi Kogyo Kaisha, Ltd.) and 50 parts byweight of heavy calcium carbonate (product name: Whiton SB Red, aproduct of Shiraishi Calcium Kaisha, Ltd.). The mixture was sufficientlykneaded and then dispersed by passing through triple paint rolls threetimes. Thereafter, the mixture was dehydrated under reduced pressure at120° C. for 2 hours and cooled to 50° C. or lower. To the mixture werethen added 4 parts by weight of vinyltrimethoxysilane (product name:A-171, a product of Momentive Performance Materials Inc.) as adehydrating agent, 3 parts by weight of γ-aminopropyltrimethoxysilane(product name: A-1110, a product of Momentive Performance MaterialsInc.) as an adhesion-imparting agent, and 0.3 parts by weight of DBU(1,8-diazabicyclo[5,4,0]undecene-7, product of Wako Pure ChemicalIndustries, Ltd.) as a condensation catalyst, and the mixture waskneaded under dehydrated conditions with substantially no water.Thereafter, the mixture was charged into a moisture-proof container(cartridge) and then hermetically packed therein to provide a one-packcurable composition. Evaluation was performed in the same way as inExample 1.

Examples 14 to 15 and Comparative Examples 13 to 14

Each curable composition was prepared in the same way as in Example 13except that the polymers (A), (B), and (C), plasticizer, filler,thixotropy-imparting agent, ultraviolet absorber, light stabilizer,dehydrating agent, adhesion-imparting agent, and catalyst were mixed atthe ratios of Examples 14 to 15 and Comparative Examples 13 to 14 shownin Tables 2 and 3. The prepared compositions were evaluated. Tables 2and 3 show their respective results.

TABLE 1 Composition (parts by weight) Mole- Back- Silyl cular bone groupComparative weight structure structure⁽¹⁾ Example 1 Example 2 Example 3Example 4 Example 5 Example 6 Example 1 Polyether (A-1) 21,100 LinearCMDMS 70 50 30 30 100 polymer (A) (A-2) 28,500 Linear CMDMS (A-3) 26,200Branched CMDMS 50 (A-4) 14,600 Linear CMDMS (A-5) 14,600 Linear MMDMS(A-6) 14,600 Linear α-type DMS 50 (A-7) 28,500 Linear CMDMS (A-8) 7,000Linear CMDMS Polyether (B-1) 21,100 Linear DMS 30 50 50 polymer (B)(B-2) 28,500 Linear DMS (B-3) 26,200 Branched DMS 70 50 (B-4) 28,500Linear DMS (B-5) 28,500 Linear TMS 70 (B-6) 7,000 Linear DMS FillerHakuenka CCR⁽²⁾ 50 50 50 50 50 50 50 Whiton SB Red⁽³⁾ 50 50 50 50 50 5050 Plasticizer DIDP⁽⁴⁾ Hexamoll DINCH⁽⁵⁾ Thixotropy- DISPARLON #6500⁽⁶⁾imparting agent Ultraviolet SUMISORB 400⁽⁷⁾ absorber Light SANOLLS-770⁽⁸⁾ stabilizer Dehydrating A-171⁽⁹⁾ 4 4 4 4 4 4 4 agent Adhesion-A-1110⁽¹⁰⁾ 3 3 3 3 3 3 3 imparting agent Catalyst DBU⁽¹¹⁾ 0.3 0.3 0.30.3 0.3 1-Phenylguanidine NEOSTANN S-1⁽¹²⁾ 0.2 TIB223⁽¹³⁾ U-220H⁽¹⁴⁾Curability Skin formation time (minutes) 20 20 35 35 15 20 15 Tensiletest TB (MPa) 1.6 1.8 2.0 1.7 2.0 2.2 1.4 (No. 3 EB (%) 280 260 250 280220 170 190 dumbbell) Composition (parts by weight) Mole- Back- Silylcular bone group Comparative Comparative Comparative ComparativeComparative weight structure structure⁽¹⁾ Example 2 Example 3 Example 4Example 5 Example 6 Polyether (A-1) 21,100 Linear CMDMS polymer (A)(A-2) 28,500 Linear CMDMS (A-3) 26,200 Branched CMDMS 100 (A-4) 14,600Linear CMDMS (A-5) 14,600 Linear MMDMS (A-6) 14,600 Linear α-type DMS100 (A-7) 28,500 Linear CMDMS (A-8) 7,000 Linear CMDMS Polyether (B-1)21,100 Linear DMS 100 polymer (B) (B-2) 28,500 Linear DMS (B-3) 26,200Branched DMS 100 (B-4) 28,500 Linear DMS (B-5) 28,500 Linear TMS 100(B-6) 7,000 Linear DMS Filler Hakuenka CCR⁽²⁾ 50 50 50 50 50 Whiton SBRed⁽³⁾ 50 50 50 50 50 Plasticizer DIDP⁽⁴⁾ Hexamoll DINCH⁽⁵⁾ Thixotropy-DISPARLON #6500⁽⁶⁾ imparting agent Ultraviolet SUMISORB 400⁽⁷⁾ absorberLight SANOL LS-770⁽⁸⁾ stabilizer Dehydrating A-171⁽⁹⁾ 4 4 4 4 4 agentAdhesion- A-1110⁽¹⁰⁾ 3 3 3 3 3 imparting agent Catalyst DBU⁽¹¹⁾ 0.3 0.30.3 0.3 1-Phenylguanidine NEOSTANN S-1⁽¹²⁾ TIB223⁽¹³⁾ U-220H⁽¹⁴⁾Curability Skin formation time (minutes) 10 10 250 150 200 Tensile testTB (MPa) 1.8 2.2 1.7 2.0 1.5 (No. 3 EB (%) 110 110 470 200 250 dumbbell)⁽¹⁾CMDMS: chloromethyldimethoxysilyl group, MMDMS:methoxymethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS:trimethoxysilyl group ⁽²⁾Fatty acid-treated precipitated calciumcarbonate (Shiraishi Kogyo Kaisha, Ltd.) ⁽³⁾Heavy calcium carbonate(SHIRAISHI CALCIUM KAISHA, LTD.) ⁽⁴⁾Diisodecyl phthalate (J-PLUS Co.,Ltd.) ⁽⁵⁾1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF)⁽⁶⁾Fatty acid amide wax (Kusumoto Chemicals, Ltd.)⁽⁷⁾2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (SumitomoChemical Company, Limited)⁽⁸⁾Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co.,Ltd.) ⁽⁹⁾Vinyltrimethoxysilane (Momentive)⁽¹⁰⁾3-Aminopropyltrimethoxysilane (Momentive)⁽¹¹⁾1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries,Ltd.) ⁽¹²⁾Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.)⁽¹³⁾Dioctyltin diacetylacetonate (TIB Chemicals AG) ⁽¹⁴⁾Dibutyltindiacetylacetonate (Nitto Kasei Co., Ltd.)

TABLE 2 Composition (parts by weight) Mole- Back- Silyl cular bone groupComparative weight structure structure⁽¹⁾ Example 7 Example 8 Example 9Example 10 Example 11 Example 12 Example 7 Polyether (A-1) 21,100 LinearCMDMS polymer (A) (A-2) 28,500 Linear CMDMS 70 100 (A-3) 26,200 BranchedCMDMS (A-4) 14,600 Linear CMDMS 50 50 (A-5) 14,600 Linear MMDMS 50 (A-6)14,600 Linear α-type DMS 50 (A-7) 28,500 Linear CMDMS 50 (A-8) 7,000Linear CMDMS 30 Polyether (B-1) 21,100 Linear DMS 50 polymer (B) (B-2)28,500 Linear DMS 50 70 (B-3) 26,200 Branched DMS (B-4) 28,500 LinearDMS 50 (B-5) 28,500 Linear TMS (B-6) 7,000 Linear DMS 30 Filler HakuenkaCCR⁽²⁾ 50 50 50 50 50 50 50 Whiton SB Red⁽³⁾ 160 160 160 160 160 160 160Plasticizer DIDP⁽⁴⁾ Hexamoll DINCH⁽⁵⁾ 30 30 30 30 30 30 30 Thixotropy-DISPARLON #6500⁽⁶⁾ 3 3 3 3 3 3 3 imparting agent Ultraviolet SUMISORB400⁽⁷⁾ 1 1 1 1 1 1 1 absorber Light SANOL LS-770⁽⁸⁾ 1 1 1 1 1 1 1stabilizer Dehydrating A-171⁽⁹⁾ 4 4 4 4 4 4 4 agent Adhesion- A-1110⁽¹⁰⁾3 3 3 3 3 3 3 imparting agent Catalyst DBU⁽¹¹⁾ 1-Phenylguanidine 0.3 0.30.3 0.3 0.3 NEOSTANN S-1⁽¹²⁾ TIB223⁽¹³⁾ 0.3 U-220H⁽¹⁴⁾ 1 Curability Skinformation time (minutes) 15 20 50 50 30 10 15 Tensile test TB (MPa) 1.52.0 1.5 1.8 1.3 2 1.5 (No. 3 EB (%) 350 200 250 220 380 150 200dumbbell) Composition (parts by weight) Mole- Back- Silyl cular bonegroup Comparative Comparative Comparative Comparative Comparative weightstructure structure⁽¹⁾ Example 8 Example 9 Example 10 Example 11 Example12 Polyether (A-1) 21,100 Linear CMDMS polymer (A) (A-2) 28,500 LinearCMDMS (A-3) 26,200 Branched CMDMS (A-4) 14,600 Linear CMDMS 100 (A-5)14,600 Linear MMDMS 100 (A-6) 14,600 Linear α-type DMS (A-7) 28,500Linear CMDMS 100 (A-8) 7,000 Linear CMDMS Polyether (B-1) 21,100 LinearDMS polymer (B) (B-2) 28,500 Linear DMS 100 (B-3) 26,200 Branched DMS(B-4) 28,500 Linear DMS 100 (B-5) 28,500 Linear TMS (B-6) 7,000 LinearDMS Filler Hakuenka CCR⁽²⁾ 50 50 50 50 50 Whiton SB Red⁽³⁾ 160 160 160160 160 Plasticizer DIDP⁽⁴⁾ Hexamoll DINCH⁽⁵⁾ 30 30 30 30 30 Thixotropy-DISPARLON #6500⁽⁶⁾ 3 3 3 3 3 imparting agent Ultraviolet SUMISORB 400⁽⁷⁾1 1 1 1 1 absorber Light SANOL LS-770⁽⁸⁾ 1 1 1 1 1 stabilizerDehydrating A-171⁽⁹⁾ 4 4 4 4 4 agent Adhesion- A-1110⁽¹⁰⁾ 3 3 3 3 3imparting agent Catalyst DBU⁽¹¹⁾ 1-Phenylguanidine 0.3 0.3 0.3 NEOSTANNS-1⁽¹²⁾ TIB223⁽¹³⁾ 0.3 U-220H⁽¹⁴⁾ 1 Curability Skin formation time(minutes) 20 30 20 50 150 Tensile test TB (MPa) 1.5 1.3 1.8 1.7 1.4 (No.3 EB (%) 110 200 250 350 110 dumbbell) ⁽¹⁾CMDMS:chloromethyldimethoxysilyl group, MMDMS: methoxymethyldimethoxysilylgroup, DMS: dimethoxymethylsilyl group, TMS: trimethoxysilyl group⁽²⁾Fatty acid-treated precipitated calcium carbonate (Shiraishi KogyoKaisha, Ltd.) ⁽³⁾Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA,LTD.) ⁽⁴⁾Diisodecyl phthalate (J-PLUS Co., Ltd.)⁽⁵⁾1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF) ⁽⁶⁾Fattyacid amide wax (Kusumoto Chemicals, Ltd.)⁽⁷⁾2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (SumitomoChemical Company, Limited)⁽⁸⁾Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co.,Ltd.) ⁽⁹⁾Vinyltrimethoxysilane (Momentive)⁽¹⁰⁾3-Aminopropyltrimethoxysilane (Momentive)⁽¹¹⁾1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries,Ltd.) ⁽¹²⁾Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.)⁽¹³⁾Dioctyltin diacetylacetonate (TIB Chemicals AG) ⁽¹⁴⁾Dibutyltindiacetylacetonate (Nitto Kasei Co., Ltd.)

TABLE 3 Composition (parts by weight) Mole- Back- Silyl cular bone groupExample Example Example Example Comparative Comparative weight structurestructure⁽¹⁾ 13 14 15 16 Example 13 Example 14 Polyether polymer (A)(A-1) 21,100 Linear CMDMS 60 60 (A-2) 28,500 Linear CMDMS (A-3) 26,200Branched CMDMS 60 (A-4) 14,600 Linear CMDMS 50 (A-5) 14,600 Linear MMDMS(A-6) 14,600 Linear α-type DMS (A-7) 28,500 Linear CMDMS (A-8) 7,000Linear CMDMS Polyether polymer (B) (B-1) 21,100 Linear DMS 60 60 (B-2)28,500 Linear DMS (B-3) 26,200 Branched DMS (B-4) 28,500 Linear DMS(B-5) 28,500 Linear TMS (B-6) 7,000 Linear DMS Acrylic polymer (C) (C-1)2,000 Linear DMS 40 40 (C-2) 2,000 Linear TMS 40 40 (C-3) 2,000 Linearα-type TMS 40 (C-4) 27,000 Linear DMS 50 Filler Hakuenka CCR⁽²⁾ 50 50 5050 50 50 Whiton SB Red⁽³⁾ 50 50 160 160 50 50 Plasticizer DIDP⁽⁴⁾ 20 2020 20 Hexamoll DINCH⁽⁵⁾ 30 30 Thixotropy-imparting agent DISPARLON#6500⁽⁶⁾ 3 3 Ultraviolet absorber SUMISORB 400⁽⁷⁾ 1 1 Light stabilizerSANOL LS-770⁽⁸⁾ 1 1 Dehydrating agent A-171⁽⁹⁾ 4 4 4 4 4 4Adhesion-imparting agent A-1110⁽¹⁰⁾ 3 3 3 3 3 3 Catalyst DBU⁽¹¹⁾ 0.3 0.30.3 1-Phenylguanidine 1 0.3 NEOSTANN S-1⁽¹²⁾ 0.2 TIB223⁽¹³⁾ U-220H⁽¹⁴⁾Curability Skin formation time (minutes) 15 35 3 20 270 60 Tensile testTB (MPa) 2.0 2.3 2.0 1.7 2.0 2.3 (No. 3 dumbbell) EB (%) 360 200 150 150390 200 ⁽¹⁾CMDMS: chloromethyldimethoxysilyl group, MMDMS:methoxymethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS:trimethoxysilyl group ⁽²⁾Fatty acid-treated precipitated calciumcarbonate (Shiraishi Kogyo Kaisha, Ltd.) ⁽³⁾Heavy calcium carbonate(SHIRAISHI CALCIUM KAISHA, LTD.) ⁽⁴⁾Diisodecyl phthalate (J-PLUS Co.,Ltd.) ⁽⁵⁾1,2-Cyclohexanedicarboxylic acid diisononyl ester (BASF)⁽⁶⁾Fatty acid amide wax (Kusumoto Chemicals, Ltd.)⁽⁷⁾2,4-Di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (SumitomoChemical Company, Limited)⁽⁸⁾Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (Sankyo Lifetech Co.,Ltd.) ⁽⁹⁾Vinyltrimethoxysilane (Momentive)⁽¹⁰⁾3-Aminopropyltrimethoxysilane (Momentive)⁽¹¹⁾1,8-Diazabicyclo[5.4.0]undecene-7 (Wako Pure Chemical Industries,Ltd.) ⁽¹²⁾Dioctyltin(bistriethoxysilicate) (Nitto Kasei Co., Ltd.)⁽¹³⁾Dioctyltin diacetylacetonate (TIB Chemicals AG) ⁽¹⁴⁾Dibutyltindiacetylacetonate (Nitto Kasei Co., Ltd.)

Comparing the results of Examples and Comparative Examples in Tables 1to 3, it is found that the mixture of the polymer (A) containing areactive silyl group having a specific structure with thedimethoxymethylsilyl- or trimethoxysilyl-terminated polymer (B) and/orthe acrylic polymer (C) exhibits favorable skin formation time andexcellent tensile properties of the cured product even when an aminecatalyst or a small amount of a dioctyltin compound was used. Asdemonstrated, however, the polymer (A) alone offers insufficientelongation of the cured product, while the polymer (B) alone slows theskin formation time.

Example 17

With 100 parts by weight in total of the polymer (A-2) (20 parts byweight) and the polymer (B-7) (80 parts by weight) were mixed 100 partsby weight of heavy calcium carbonate (product name: Whiton SB Red, aproduct of Shiraishi Calcium Kaisha, Ltd.) and 2 parts by weight ofhydrophilic fumed silica (product name: Aerosil 200, a product of NipponAerosil Co., Ltd.). The mixture was sufficiently kneaded and thendispersed by passing through triple paint rolls once. Subsequently, themixture was kneaded for 2 hours while dehydrated under reduced pressureconditions of 0.2 mmHg at 120° C. using a planetary mixer. After coolingto room temperature, 2 parts by weight of vinyltrimethoxysilane as adehydrating agent, 2 parts by weight of γ-aminopropyltrimethoxysilane asan adhesion-imparting agent, 5 parts by weight of 1-o-tolylbiguanide asa condensation catalyst, and 0.3 parts by weight of dibutyltin dilaurate(product name: NEOSTANN U-100, produced by Nitto Kasei Co., Ltd.) wereadded to the mixture and the mixture was kneaded under dehydratedconditions with substantially no water. Thereafter, the mixture wascharged into a moisture-proof container (cartridge) and thenhermetically packed therein to provide a one-pack curable composition.

(Evaluation)

The initial tack properties and adhesion of the prepared compositionswere determined by the following methods.

(Initial Tack)

Tack Development Time and Tack Time

Each prepared composition was applied to a slate plate by combing.Thereafter, the state of the applied composition was observed by afinger touch. The time point at which the finger felt a resistance whenit was released from the composition was regarded as the tackdevelopment time. The time period during which this resistance continuedwas regarded as the tack time.

Initial Holding Power (Tack Strength)

Each prepared composition was applied to a slate plate by combing. Avinyl floor sheet (PERMALEUM, a product of Tajima, Inc.) having a lengthof 200 mm and a width of 25 mm was laminated thereto. The vinyl floorsheet used was in advance wrapped, with its backside facing inward,around a PVC pipe having a radius of 25 mm and thereby deformed. Afterthe lamination of this vinyl floor sheet, the laminate was left for awhile. The tack strength was assessed as being poor (x) when the vinylfloor sheet arched up and separated. The tack strength was assessed asbeing good (◯) when the vinyl floor sheet stayed laminated withoutarching up.

(Adhesion Strength)

Each prepared composition was applied to a slate plate by combingaccording to JIS A5536, and an open time was taken until tack wasdeveloped. Thereafter, a vinyl floor sheet (PERMALEUM, a product ofTajima, Inc.) having a length of 200 mm and a width of 25 mm waslaminated thereto. The laminate was left at 23° C. for 1 week and thensubjected to a tensile test (tensile rate: 200 mm/min) in a peelingdirection at 90° to determine the adhesion strength.

Examples 18 to 23 and Comparative Examples 15 to 20

Each curable composition was prepared in the same way as in Example 18except that the polymers (A), (B), and (C), filler, dehydrating agent,adhesion-imparting agent, and catalyst were mixed at the ratios ofExamples 18 to 23 and Comparative Examples 15 to 20 shown in Tables 4and 5. The prepared compositions were evaluated. Tables 4 and 5 showtheir respective results.

TABLE 4 Composition (parts by weight) Mole- Back- Silyl cular bone groupExample Example Comparative Comparative weight structure structure⁽¹⁾ 1718 Example 15 Example 16 Polyether polymer (A) (A-2) 28,500 Linear CMDMS20 20 100 100 Polyether polymer (B) (B-2) 28,500 Linear DMS 50 (B-7)14,500 Linear DMS 80 (B-8) 4,200 Linear DMS 30 Filler Aerosil 200⁽²⁾ 2 22 2 Whiton SB Red⁽³⁾ 100 100 100 100 Dehydrating agent A-171⁽⁴⁾ 2 2 2 2Adhesion-imparting agent A-1110⁽⁵⁾ 2 2 2 2 Catalyst 1-o-Tolylbiguanide 55 5 5 NEOSTANN U-100⁽⁶⁾ 0.3 0.3 0.3 Viscosity (Pa · S) 410 190 490 480Tack development time (minutes) 15 15 10 10 Initial holding power (Tackstrength) ◯ ◯ ◯ ◯ Tack time (minutes) 15-110 15-100 10-20 10-20 Peeladhesion strength (N/25 mm) 27 24 20 21 ⁽¹⁾CMDMS:chloromethyldimethoxysilyl group, DMS: dimethoxymethylsilyl group, TMS:trimethoxysilyl group ⁽²⁾Hydrophilic fumed silica (Nippon Aerosil Co.,Ltd.) ⁽³⁾Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA, LTD.)⁽⁴⁾Vinyltrimethoxysilane (Momentive)⁽⁵⁾N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Momentive)⁽⁶⁾Dibutyltin dilaurate (Nitto Kasei Co., Ltd.)

TABLE 5 Composition (parts by weight) Compar- Compar- Compar- Compar-Molec- Back- Silyl ative ative ative ative ular bone group Exam- Exam-Exam- Exam- Exam- Exam- Exam- Exam- Exam- weight structure structure⁽¹⁾ple 19 ple 20 ple 21 ple 22 ple 23 ple 17 ple 18 ple 19 ple 20 Polyether(A-2) 28,500 Linear CMDMS 30 30 30 100 20 polymer (A) Polyether (B-1)21,100 Linear DMS 70 70 70 70 70 70 polymer (B-5) 28,500 Linear TMS 3020 20 (B) (B-7) 14,500 Linear DMS 80 80 80 Acrylic (C-5) 3,000 LinearDMS 30 30 30 30 30 polymer (C-6) 3,000 Linear TMS 30 30 (C) (C′-7) 3,000Linear — 30 30 Filler Aerosil 200⁽²⁾ 2 2 2 2 2 2 2 2 2 Whiton SB Red⁽³⁾100 100 100 100 100 100 100 100 100 Dehy- A-171⁽⁴⁾ 2 2 2 2 2 2 2 2 2drating agent Adhesion- A-1110⁽⁵⁾ 2 2 2 2 2 2 2 2 2 imparting agentCatalyst 1-o-Tolylbiguanide 5 5 5 5 5 5 5 5 NEOSTANN U-100⁽⁶⁾ 0.3 0.30.3 0.3 0.3 0.3 0.3 0.3 0.3 Tack development time (minutes) 15 10 10 520 150 50 60 60 Initial holding power (tack strength) ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯ ◯Tack time (minutes) 15-220 10-190 10-310 5-100 20-220 150-170 50-8060-80 60-80 Peel adhesion strength (N/25 mm) 34 32 38 30 35 31 29 24 26⁽¹⁾CMDMS: chloromethyldimethoxysilyl group, DMS: dimethoxymethylsilylgroup, TMS: trimethoxysilyl group ⁽²⁾Hydrophilic fumed silica (NipponAerosil Co., Ltd.) ⁽³⁾Heavy calcium carbonate (SHIRAISHI CALCIUM KAISHA,LTD.) ⁽⁴⁾Vinyltrimethoxysilane (Momentive)⁽⁵⁾N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (Momentive)⁽⁶⁾Dibutyltin dilaurate (Nitto Kasei Co., Ltd.)

Comparing the results of Examples and Comparative Examples in Tables 4and 5, it is found that the mixture of the polymer (A) containing areactive silyl group having a specific structure and the polymer (B)(and the polymer (C)) develops tack rapidly and keeps it for a very longperiod of time and is thus excellent as contact adhesive. In addition,the tack strength thus developed is sufficiently high for practical use.On the other hand, compositions containing components other than thecombinations of the polymers according to the present invention fail tohave tack strength suitable for practical use, or have a tack timeshorter than that of the compositions of the present invention.

INDUSTRIAL APPLICABILITY

The curable composition of the present invention comprising the reactivesilyl group-containing polyether polymer (A), and the reactive silylgroup-containing polyether polymer (B) and/or the reactive silylgroup-containing (meth)acrylic polymer has excellent elongationproperties and rapid curability and is also excellent in initial tackproperties.

The invention claimed is:
 1. A curable composition, comprising: apolyether polymer (A) containing a reactive silyl group represented bythe following formula (1); and at least one of a polyether polymer (B)containing a reactive silyl group represented by the following formula(2) and a (meth)acrylic polymer (C) containing a reactive silyl grouprepresented by the following formula (3):—W—CH₂—SiR¹ _(a)R² _(b)X_(c)   (1) wherein R¹ is a methoxymethyl group;R² represents a C1 to C20 hydrocarbon group, a C6 to C20 aryl group, aC7 to C20 aralkyl group, or a triorganosiloxy group represented by R⁰₃SiO— wherein each of three R⁰s is a C1 to C20 hydrocarbon group andthey may be the same as or different from each other; X represents ahydroxy or hydrolyzable group; W represents a linking group selectedfrom —O—R⁸—, —O—CO—N(R⁹)—, —N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—,—NH—CO—S—, and —S— wherein R⁸ represents a divalent C1 to C8 hydrocarbongroup, and R⁹ represents hydrogen or a C1 to C18 hydrocarbon groupoptionally substituted with halogen; in the case that W is —O—R⁸—, a is1 or 2, b is 0 or 1, and c is 1 or 2, provided that a+b+c =3 issatisfied; in the case that W is a group other than —O—R⁸-, a is 0, 1,or 2, b is 0, 1, or 2, and c is 1, 2, or 3, provided that a+b+c=3 issatisfied; and in the case that a plurality of R¹s, R²s, or Xs exist,they may be the same as or different from each other,—V—SiR² _(d)X_(3-d)   (2) wherein R² and X are defined as mentioned informula (1); V represents a divalent C2 to C8 hydrocarbon group; drepresents any of 0, 1, and 2; and in the case that a plurality of R²sor Xs exist, they may be the same as or different from each other, and—Z—(CH₂)_(n)—SiR¹ _(a)R² _(b)X_(c)   (3) wherein R¹, of Formula (3) is aC1 to C20 hydrocarbon group wherein at least one hydrogen atom on carbonatoms at positions 1 to 3 is replaced with halogen, —OR³, —NR⁴R⁵, —N═R⁶,—SR⁷ (in which each of R³, R⁴, R⁵, and R⁷ is a hydrogen atom or a C1 toC20 substituted or unsubstituted hydrocarbon group, and R⁶ is a divalentC1 to C20 substituted or unsubstituted hydrocarbon group), a C1 to C20perfluoroalkyl group, or a cyano group; R², and X are defined asmentioned in formula (1); Z represents a linking group selected from—CO—O—, —O—CO—N(R⁹)—, —N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—,—NH—CO—S—, and —S— wherein R⁹ is defined as mentioned in formula (1); nrepresents a number of 1 to 8; a is 0,1, or 2, b is 0, 1, or 2, and c is1, 2, or 3, provided that the condition: a+b+c =3 is satisfied; and inthe case that a plurality of R¹s, R²s, or Xs exist, they may be the sameas or different from each other.
 2. The curable composition according toclaim 1, wherein W in formula (1) is —O—R⁸— wherein R⁸ is a divalent C1to C8 hydrocarbon group.
 3. The curable composition according to claim1, wherein the polyether polymer (A) is a polyoxypropylene polymer. 4.The curable composition according to claim 1, wherein the polyetherpolymer (A) is a linear polymer having no branch.
 5. The curablecomposition according to claim 1, wherein a backbone structure of thepolyether polymer (B) is a polyoxypropylene polymer.
 6. The curablecomposition according to claim 1, wherein the reactive silyl group offormula (2) is a dimethoxymethylsilyl group.
 7. The curable compositionaccording to claim 1, wherein the (meth)acrylic polymer (C) is at leastone of a reactive silyl group-containing alkyl (meth)acrylate polymerand copolymer.
 8. A curable composition, which comprises a polyetherpolymer (A) containing a reactive silyl group represented by thefollowing formula (1); a polyether polymer (B) containing a reactivesilyl group represented by the following formula (2); and a(meth)acrylic polymer (C) containing a reactive silyl group representedby the following formula (3):—W—CH₂—SiR¹ _(a)R² _(b)X_(c)   (1) wherein R¹ is a C1 to C20 hydrocarbongroup wherein at least one hydrogen atom on carbon atoms at positions 1to 3 is replaced with halogen, —OR³, —NR⁴R⁵, —N═R⁶, —SR⁷ (in which eachof R³, R⁴, R⁵, and R⁷ is a hydrogen atom or a C1 to C20 substituted orunsubstituted hydrocarbon group, and R⁶ is a divalent C1 to C20substituted or unsubstituted hydrocarbon group), a C1 to C20perfluoroalkyl group, or a cyano group; R² represents a C1 to C20hydrocarbon group, a C6 to C20 aryl group, a C7 to C20 aralkyl group, ora triorganosiloxy group represented by R⁰ ₃SiO— wherein each of threeR⁰s is a C1 to C20 hydrocarbon group and they may be the same as ordifferent from each other; X represents a hydroxy or hydrolyzable group;W represents a linking group selected from —O—R⁸—, —O—CO—N(R⁹)—,—N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—, —S—CO—NH—, —NH—CO—S—, and —S— wherein R⁸represents a divalent C1 to C8 hydrocarbon group, and R⁹ representshydrogen or a C1 to C18 hydrocarbon group optionally substituted withhalogen; in the case that W is —O—R⁸—, a is 1 or 2, b is 0 or 1, and cis 1 or 2, provided that a+b+c =3 is satisfied; in the case that W is agroup other than —O—R⁸—, a is 0, 1, or 2, b is 0, 1, or 2, and c is 1,2, or 3, provided that a+b+c =3 is satisfied; and in the case that aplurality of R¹s, R²s, or Xs exist, they may be the same as or differentfrom each other,—V—SiR² _(d)X_(3-d)   (2) wherein R² and X are defined as mentioned informula (1); V represents a divalent C2 to C8 hydrocarbon group; drepresents any of 0, 1, and 2; and in the case that a plurality of R²sor Xs exist, they may be the same as or different from each other, and—Z—(CH₂)_(n)—SiR¹ _(a)R² _(b)X_(c)   (3) wherein R¹, R², and X aredefined as mentioned in formula (1); Z represents a linking groupselected from —CO—O—, —O—CO—N(R⁹)—, —N(R⁹)—CO—O—, —N(R⁹)—CO—N(R⁹)—,—S—CO—NH—, —NH—CO—S—, and —S— wherein R⁹ is defined as mentioned informula (1); n represents a number of 1 to 8; a is 0, 1, or 2, b is 0,1, or 2, and c is 1, 2, or 3, provided that the condition: a+b+c =3 issatisfied; and in the case that a plurality of R¹s, R²s, or Xs exist,they may be the same as or different from each other.
 9. The curablecomposition according to claim 8, wherein the polyether polymer (A) hasa number average molecular weight of 22,000 or higher.
 10. The curablecomposition according to claim 8, wherein the polyether polymer (A) andthe polyether polymer (B) are contained at a ratio of (A):(B)=50:50 to5:95 (parts by weight).
 11. The curable composition according to claim8, further comprising: at least one of an amine compound (d1) and anorganic dialkyltin compound (d2) as a condensation catalyst (D).
 12. Asealing material, comprising the curable composition according to claim8 as a component.
 13. An adhesive, comprising the curable compositionaccording to claim 8 as a component.
 14. A contact adhesive, comprisingthe curable composition according to claim 8 as a component.
 15. Thecontact adhesive according to claim 8, comprising the polyether polymer(A) and the polyether polymer (B).
 16. A cured product, obtained bycuring the curable composition according to claim
 8. 17. A contactadhesive, comprising the curable composition according to claim 1 as acomponent.
 18. The contact adhesive according to claim 17, comprisingthe polyether polymer (A) and the polyether polymer (B).